Pd(II)-Catalyzed Directing-Group-Aided C–H Arylation and Alkylation of Pyrene Core: Synthesis of C1,C2- and C1,C10-Disubstituted Pyrene Motifs

Abstract

We report the application of the Pd(II)-catalyzed, directing-group-aided C–H arylation/alkylation tactics to functionalize the pyrene core, especially, the relatively inaccessible C2 and K-region C10 positions of the pyrene core and augmentation of the library of pyrene derivatives with C1,C2- and C1,C10-disubstituted pyrene motifs. The Pd(II)-catalyzed β-C–H arylation/alkylation of the C2-position of pyrene-1-carboxamide possessing an 8-aminoquinoline directing group yielded various C1,C2-disubstituted pyrenes. Similarly, the Pd(II)-catalyzed selective γ-C–H arylation/alkylation of the C10-position of N-(pyren-1-yl)picolinamide, possessing a picolinamide directing group, yielded various C1,C10-disubstituted pyrenes. Examples of C(9)–H arylation of pyrene-1-carboxamide and the removal of the directing group after the C–H arylation/alkylation reactions were also shown. The structures of representative pyrene derivatives were confirmed by the X-ray structure analysis. Given the importance of the pyrene derivatives in various fields of chemical sciences, this report is a contribution towards augmentation of the library of pyrene derivatives with C1,C2- and C1,C10-disubstituted pyrene amide motifs.

Key words

C–H activation - C–H arylation/alkylation - C–H functionalization - bidentate directing group - carboxamides - palladium - pyrene

During an era when cross-coupling reactions were ubiquitous in organic synthesis,[1] [2] there were some pioneering efforts at direct functionalization of C–H bonds in small organic molecules to achieve C–C bond construction. In 1955 and 1956 Murahashi reported[3] the cobalt-promoted insertion of carbon monoxide into an ortho-C(sp²)–H bond of aldimine and azobenzene substrates. Subsequently, various stoichiometric metal-promoted C–H bond activation reactions involving cyclometallated species were published.[4] In 1970, the palladium-catalyzed chlorination of an ortho-C(sp²)–H bond of azobenzene reported by Fahey is another important discovery.[5] Subsequently, Jordan (1989), Moore (1992) and Murai (1993) reported breakthroughs in catalytic C–H activation/functionalization methods involving Zr- and Ru-based catalysts.[6] [7] [8] During the last 20 years, research on transition-metal-catalyzed C–H bond activation reactions has advanced at a rapid rate.[9] [10] [11]

Pertinently, the transition-metal-catalyzed sp²/sp³ C–H activation/functionalization is considered to be a remarkable synthetic strategy to functionalize small organic molecules. The catalytic C–H functionalization of sp²/sp³ C–H bonds of small organic molecules has been accomplished with or without the help of a directing group.[9] [10] [11] [12] [13] [14] [15] In particular, directing-group-aided sp² and sp³ C–H activation/functionalization strategies have received significant attention in organic synthesis because the strategy makes it feasible to functionalize the required substrates with site-selectivity or regioselectivity as well as stereoselectivity. Along this line, the Pd(II)-catalyzed bidentate directing group (BDG)-aided site-selective sp² and sp³ C–H activation/functionalization of carboxamides are considered benchmark strategies.[11] [12] [13] [14] [15] The site-selective C–H functionalization of carboxamides derived from carboxylic acid substrates were achieved with the help of 8-aminoquinoline type BDGs (introduced by Daugulis).[11] [12] [13] [14] [15] On the other hand, the site-selective C–H functionalization of carboxamides derived from amine substrates were achieved with the help of picolinamide type BDGs.[11] [12] [13] [14] [15]

Due to the superior fluorescence properties, efficient excimer emission, and high charge-carrier mobility, pyrene and its derivatives have received much attention in various fields of chemical sciences including organic-, supramolecular and materials chemistry.[16] [17] [18] [19] Markedly, pyrenes are important building blocks to assemble materials such as organic light-emitting diodes (OLEDs), organic semiconducting materials for OFETs, supramolecular sensors, and solar cells. Almost all types of photoelectric devices have been investigated using various pyrene-based organic materials.[16b–d] ^, [18] It is documented that the optoelectronic and photophysical properties of pyrenes are strongly dependent on the respective substituents and their positions.[16,17,19] Consequently, several methodologies have been developed to functionalize the multiple reactive positions of pyrene core.[16] [17]

Figure 1 K-Region and non-K-region of the pyrene motif

Scheme 1 Theme of this work: C–H arylation/alkylation of pyrene amide­ motifs

The 1-, 3-, 6- and 8-positions of pyrene are known as ‘active/common sites’ and these sites have electron-rich density and readily undergo electrophilic aromatic substitution (S_EAr) reactions.[16b] Generally, pyrene derivatives have been synthesized by introducing substitutions at these active/common sites. The 2- and 7-positions of pyrene are known as ‘nodal plane positions and uncommon or inaccessible sites’ and these are relatively difficult to functionalize (Figure [1]).[16b] It may be noted that the Friedel–Crafts tert-butylation and Ir-catalyzed direct borylation reactions have been carried out at these positions. The 4-, 5-, 9- and 10-positions of pyrene are known as ‘the K-region sites’ and it may be noted that oxidation and Pd-catalyzed oxidative direct arylation reactions have been carried out at these positions and these results have been summarized by Feng and Yamato.[16b]

Table 1 Optimization of the C–H Arylation of Pyrene Carboxamide 2a and Assembly of the C1,C2-Disubstituted Pyrene Motif 4a

Entry	Catalyst	Additive	Solvent	T (°C)	Yield of 4a (%)
1	Pd(OAc)2	Ag2CO3	o-xylene	135	38
2	Pd(OAc)2	Cs2CO3	o-xylene	135	40
3	Pd(OAc)2	K2CO3	o-xylene	135	51
4	Pd(OAc)2	AgOAc	o-xylene	135	70
5	Pd(OAc)2	AgOAc	1,2-DCE	130	65
6a	Pd(OAc)2	AgOAc	o-xylene	130	22
7b	Pd(OAc)2	AgOAc	o-xylene	130	35
8c	Pd(OAc)2	AgOAc	o-xylene	130	47
9	Pd(TFA)2	AgOAc	o-xylene	130	60
10	Pd(MeCN)2Cl2	AgOAc	o-xylene	130	53
11	Ni(OTf)2	NaHCO3	toluene	160	15

^a 0.2 mmol of 3a.

^b 0.4 mmol of 3a.

^c 0.6 mmol of 3a.

Impressed by the chemical transformations carried out on the pyrene core and driven by the importance of the pyrene derivatives in chemical sciences,[15] [16] [17] [18] [19] we intended to take forward the functionalization of the pyrene core through the directing-group-aided C–H functionalization route to assemble new pyrene amide motifs. A few instances of functionalization of the pyrene core through the directing-group-aided C–H functionalization have been reported. Nevertheless, the available reports provided only single examples of functionalization of the pyrene core (Scheme [1]).[15] We wanted to contribute to the development of this field by performing the bidentate directing-group-aided site-selective C–H arylation and alkylation of the relatively inaccessible C2 position and K-region C10 position of pyrene amides 2a and 2b, respectively. To our knowledge, the bidentate directing-group-aided site-selective C–H arylation and alkylation C2 position and C10 position of pyrene amides have not yet been explored. In a continuation of our interest in C–H activation reactions, herein we report the Pd(II)-catalyzed, directing-group-aided arylation/alkylation of C(2)–H bond of pyrene-1-carboxamide motif 2a linked with 8-aminoquinoline DG, and C(10)–H bond of 1-aminopyrene motif 2b linked with a picolinamide DG, and the assembly of various C1,C2- and C1,C10-disubstituted pyrene amide motifs.

Starting with the assembly of C1,C2- and C1,C10-disubstituted pyrene motifs via the Pd(II)-catalyzed, directing-group-aided C–H arylation/alkylation reaction, initially we prepared the pyrene-1-carboxamide 2a possessing 8-aminoquinoline directing group, which enabled the selective β-C(sp²)–H functionalization of 2a (C2-position, Table [1]). We performed optimization reactions by employing the standard Pd(II)-catalyzed sp² β-C–H arylation conditions.[11] [12] [13] Typically, the directing group 8-aminoquinoline-aided C–H functionalization of carboxamides have been carried out by using a Pd(II) catalyst and an additive such as AgOAc or Ag₂CO­₃ or K₂CO₃, which function as a halide ion scavenger.[11] [12] [13]

First, a mixture of pyrene-1-carboxamide 2a, ArI (3a) and Pd(OAc)₂ catalyst (10 mol%) in the presence of Ag₂CO₃ as an additive in o-xylene was heated at 135 °C for 24 h, which yielded the C(2)–H arylated pyrene-1-carboxamide 4a in satisfactory yield (38%, Table [1], entry 1). Next, the same reaction was carried out in the presence of Cs₂CO₃ as an additive instead of Ag₂CO₃ and this reaction also yielded the C(2)–H arylated pyrene-1-carboxamide 4a in satisfactory yield (40%, entry 2).

Scheme 2 Assembly of C1,C2-disubstituted pyrene carboxamide motifs 4a–q via the Pd(II)-catalyzed, 8-aminoquinoline-directed C–H arylation of 2a

The Pd(II)-catalyzed arylation of pyrene-1-carboxamide 2a by using K₂CO₃ as an additive yielded the C(2)–H arylated pyrene-1-carboxamide 4a in an improved yield (51%, Table [1], entry 3). The Pd(II)-catalyzed arylation of 2a in the presence of AgOAc as an additive in o-xylene or 1,2-DCE at 130–135 °C yielded 4a in 65–70% yields (entries 4 and 5). The Pd(II)-catalyzed arylation of 2a by using different amounts of 3a (1–3 equiv) yielded the product 4a in 22–47% yields (entries 6–8). The arylation of 2a by using different palladium catalysts such as Pd(TFA)₂ and Pd(MeCN)₂Cl₂ yielded the product 4a in 53–60% yields (entries 9 and 10). The C–H arylation of 2a under the Ni(OTf)₂-catalyzed reaction conditions yielded 4a in only 15% yield (entry 11).

Having the optimized reaction conditions in hand for the Pd(II)-catalyzed C(2)–H arylation of 2a, we wanted to enrich the library of pyrene-1-carboxamide via the Pd(II)-catalyzed C(2)–H arylation reaction. Towards this, we carried out the Pd(II)-catalyzed C(2)–H arylation of 2a using a variety of aryl iodides (Scheme [2]). Arylation of 2a with aryl iodides containing different electron-withdrawing substituents (e.g., Ac, NO₂, COOMe and Cl) at the para-position yielded the corresponding C(2)–H arylated pyrene-1-carboxamides 4a–d in moderate to good yields (53–86%, Scheme [2]). Next, the Pd(II)-catalyzed C(2)–H arylation of pyrene-1-carboxamide 2a with 6-iodo-2,3-dihydrobenzo[b][1,4]dioxine, PhI and aryl iodides containing different electron-donating substituents (e.g., Et, i-Pr, Me and OMe) at the para-position yielded the corresponding C(2)–H arylated pyrene-1-carboxamides 4e–j in moderate to good yields (45–71%, Scheme [2]).

Scheme 3 Assembly of C1,C10-disubstituted pyrene carboxamide motifs 5a–t via the Pd(II)-catalyzed, picolinamide-directed C–H arylation of 2b

We then performed the Pd(II)-catalyzed C(2)–H arylation of pyrene-1-carboxamide 2a with aryl iodides containing different electron-donating or electron-withdrawing substituents (e.g., OMe, Me, Cl and F) at the meta-position, which yielded the corresponding C(2)–H arylated pyrene-1-carboxamides 4k–n in 66–84% yields (Scheme [2]). Furthermore, the Pd(II)-catalyzed C(2)–H arylation of pyrene-1-carboxamide 2a with different heteroaryl iodides also yielded the corresponding C(2)–H arylated pyrene-1-carboxamides 4o–q in satisfactory to moderate yields (48–58%, Scheme [2]). The structures of representative pyrene derivatives 4a and 4e were confirmed by the X-ray structure analysis (Figure [2]).

Figure 2 X-ray (ball and stick model) crystal structures of compounds 4a, 4e, 5n and 12c

Scheme 4 Assembly of pyrene carboxamide motifs 6a,b and 8a,b via the Pd(II)-catalyzed C–H arylation of 2c,d

After assembling various C(2)–H arylated pyrene-1-carboxamides 4a–q, we then planned to expand the scope of this work and enrich the library of 1-aminopyrene core by assembling various C(10)–H arylated 1-aminopyrene-based motifs (Scheme [3]). Towards this end, we prepared N-(pyren-1-yl)picolinamide (2b), possessing a picolinamide directing group, which will enable the γ-C(sp²)–H functionalization of 2b at the C10-position. We then performed the Pd(II)-catalyzed C(10)–H arylation of 2b by using a variety of aryl iodides (Scheme [3]). The Pd(II)-catalyzed C(10)–H arylation of 2b with aryl iodides containing different electron-donating or electron-withdrawing substituents (e.g., OMe, Me, F, COOEt and Ac) at the meta-position yielded the corresponding C(10)–H arylated N-(pyren-1-yl)picolinamides 5a–e in moderate to good yields (57–71%, Scheme [3]).

The Pd(II)-catalyzed C(10)–H arylation of 2b with PhI and various aryl iodides containing different electron-donating and electron withdrawing substituents (e.g., OMe, Me, OEt, Ac, COOMe, CN, Cl and Br) at the para-position yielded the corresponding C(10)–H arylated N-(pyren-1-yl)picolinamides 5f–n in moderate to good yields (50–64%, Scheme [3]). The Pd(II)-catalyzed C(10)–H arylation of 2b with disubstituted aryl iodides and 6-iodo-2,3-dihydrobenzo[b][1,4]dioxine yielded the corresponding C(10)–H arylated N-(pyren-1-yl)picolinamides 5o–q in satisfactory to good yields (45–65%, Scheme [3]). Furthermore, the C(10)–H arylation of 2b with different heteroaryl iodides also yielded the corresponding C(10)–H arylated N-(pyren-1-yl)picolinamides 5r–t in satisfactory to good yields (42–71%, Scheme [3]). The structure of representative pyrene carboxamide 5n was confirmed by X-ray crystal structure analysis (Figure [2]).

We then explored the possibility of using other directing groups similar to 8-aminoquinoline. Accordingly, we prepared the pyrene-1-carboxamide 2d, possessing 2-(methylthio)aniline as the directing group[11] (Scheme [4]). We then performed the Pd(II)-catalyzed C(10)–H arylation of 2d with different aryl iodides (Scheme [4]), which also afforded the corresponding products 6a,b in 56–57% yields. Furthermore, we also attempted the functionalization at the C9-position of the pyrene core by using the procedure reported by Yang and You for the 1-naphthylamine system.[10l] In this regard, we treated pyrene-1-carboxamide 2c with p-tolylboronic acid in the presence of the Pd(OAc)₂ catalyst and NFSI as an additive in 1,2-DCE at 90 °C for 24 h, which afforded the corresponding C(9)–H arylated pyrene-1-carboxamide 8a in 53% yield (Scheme [4]). Similarly, the reaction of pyrene-1-carboxamide 2c with phenylboronic acid in the presence of the Pd(OAc)₂ catalyst and NFSI as an additive in 1,2-DCE at 90 °C for 24 h afforded the C(9)–H arylated pyrene-1-carboxamides 8b in 55% yield (Scheme [4]).

To further extend the substrate scope and enrich the library of pyrene-1-carboxamide and 1-aminopyrene core, we attempted the Pd(II)-catalyzed alkylation of C(2)–H and C(10)–H bonds of pyrene amides 2a and 2b, respectively. Towards this, we carried out the Pd(II)-catalyzed C(2)–H alkylation of pyrene-1-carboxamide 2a with different alkyl iodides, which successfully yielded the corresponding C(2)–H alkylated pyrene-1-carboxamides 10a–d in good yields (70–74%, Scheme [5]). Similarly, the Pd(II)-catalyzed C(10)–H alkylation of N-(pyren-1-yl)picolinamide (2b) with different alkyl iodides yielded the corresponding C(10)–H alkylated N-(pyren-1-yl)picolinamide 11a–c in good yields (58–88%, Scheme [5]).

Scheme 5 Assembly of C1,C2- and C1,C10-disubstituted pyrene carboxamide­ motifs 10a–d and 11a–c via C–H alkylation of the pyrene core

We also attempted the removal of the directing group after the C–H arylation of the pyrene amides. In this regard, the C(10)–H arylated N-(pyren-1-yl)picolinamide 5f was subjected to different amide hydrolysis conditions. Of the limited number of attempts that were carried out, we found that heating a mixture of N-(pyren-1-yl)picolinamide 5f and NaOH in EtOH/H₂O at 90 °C for 24 h yielded the C(10)–H arylated 1-aminopyrene derivative 12a in 56% yield (Scheme [6]). Similarly, the NaOH-mediated hydrolysis of the C–H arylated N-(pyren-1-yl)picolinamides 5g,t yielded the corresponding C(10)–H arylated 1-aminopyrene derivatives 12b,c in 70–73% yields (Scheme [6]). Finally, compound 12d was obtained via one-pot sequential C–H arylation of 2b under standard reaction conditions and neat conditions followed by NaOH-mediated hydrolysis (Scheme [6]). The structures of representative pyrene derivative 12c was unequivocally established by X-ray crystal structure analysis (Figure [2]).[20]

Scheme 6 Trials on the removal of the directing group and one-pot sequential C–H arylation of pyrene carboxamide 2b followed by directing group removal

In summary, we have shown the application of the Pd(II)-catalyzed, directing-group-aided C–H arylation/alkylation tactics to functionalize the relatively inaccessible C2 and K-region C10 positions of the pyrene core. The Pd(II)-catalyzed β-C–H arylation/alkylation of the C2-position of pyrene-1-carboxamide, possessing an 8-aminoquinoline directing group, afforded various C1,C2-disubstituted pyrene motifs. Similarly, the Pd(II)-catalyzed selective γ-C–H arylation/alkylation of the C10-position of N-(pyren-1-yl)picolinamide possessing a picolinamide directing group afforded various C1,C10-disubstituted pyrene motifs. Examples of C(9)–H arylation of pyrene-1-carboxamide and the removal of the directing group after the C–H arylation reactions were also shown. The structures of representative pyrene derivatives were confirmed by X-ray crystal structure analysis. Given the importance of the pyrene derivatives in various fields of chemical sciences, this report is a contribution towards augmentation of the library of pyrene derivatives with C1,C2- and C1,C10-disubstituted pyrene amide motifs. While we have obtained a library of new C1,C2- and C1,C10-disubstituted pyrene amide motifs, currently, we are studying their structure and photophysical properties and exploring their application, the results of which will be reported in due course.

¹H and ¹³C{¹H} NMR spectra of compounds were recorded (using TMS as an internal standard) with 400 or 500 and ca. 101 or ca. 126 MHz spectrometers, respectively. The HRMS analysis data of samples were obtained with a QTOF mass analyzer by using electrospray ionization (ESI) method. IR spectra of samples were recorded as neat or thin films. Column chromatography purification was carried out on silica gel (100–200 mesh). Reactions were conducted in anhydrous solvents under a nitrogen atmosphere when required. Organic layers obtained after workup were dried by using anhydrous Na₂SO₄. Thin-layer chromatography (TLC) analyses were performed on silica gel (silica gel 60 F₂₅₄ plates) or alumina plates and components were visualized by observation under irradiation with a UV lamp or iodine vapor. Isolated yields of all the products are reported. Yields of isolated compounds were not optimized. In all of the cases, after the Pd(II)-catalyzed reactions, the respective crude reaction mixtures were subjected to the column chromatographic purification to afford the pure samples. Some pyrene amide products contain some inseparable adventitious grease and hexane residuals or adventitious moisture peaks in the ¹H/¹³C NMR spectra. Adventitious grease and hexane residuals seem to get trapped with the pyrene amide compounds during handling/sample purification. While we have tried to purify all the samples to get pure compounds, the C–H functionalized pyrene compounds and the starting material pyrene compounds have similar R_f values and thus, their separation in column chromatography was found to be a difficult task. Accordingly, we have repeated column chromatography purification for most of the cases to obtain samples with the highest possible purity.

Synthesis of Carboxamides 2a, 2c, 2d; General Procedure

A dry round-bottomed flask containing amine (9 mmol, 0.9 equiv) and Et₃N (11 mmol, 1.1 equiv) was stirred for 5–10 min under a nitrogen atmosphere. To the reaction flask was then added anhydrous DCM (20 mL) followed by dropwise addition of the corresponding acid chloride, which was prepared from pyrene-1-carboxylic acid (10 mmol) and SOCl₂ (9 equiv) after refluxing for 12 h. The reaction mixture was then stirred overnight and, after this period, the reaction mixture was diluted with DCM (10–15 mL) and washed with water (10–15 mL) and twice with saturated aqueous NaHCO₃ solution (10–15 mL). The combined organic layers were washed with 1 N HCl (2 × 20 mL) to remove excess amine, then dried over anhydrous Na₂SO₄, and concentrated under vacuum to afford the corresponding carboxamides.

Synthesis of Carboxamide 2b

An appropriate amount of picolinic acid (10 mmol), N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride (1.1 equiv), 1-hydroxybenzotriazole hydrate (1.1 equiv) in DCM (20 mL) was stirred for 1 h at 0 °C under a nitrogen atmosphere. Then, an appropriate amount of 1-aminopyrene (1 equiv) was added to the above mixture and stirred for 16–24 h at room temperature. The resulting solution was then subjected to aqueous workup and washed with aqueous NaHCO₃ solution (two times). The resulting solution mixture was concentrated and purified on silica gel column chromatography (EtOAc­/hexane) to give the corresponding carboxamide.

Pd(II)-Catalyzed Arylation of Carboxamides 2a/2d and Preparation of Compounds 4/6

A mixture of an appropriate carboxamide (0.2 mmol, 1 equiv), an appropriate aryl iodide (0.8 mmol, 4 equiv), Pd(OAc)₂ (4.5 mg, 10 mol%) and AgOAc (0.44 mmol, 2.0–2.2 equiv) in o-xylene (2 mL) was heated at 130 °C for 24 h in a 10 mL capacity sealed (pressure) tube (the pressure tube was flushed with nitrogen atmosphere for 2 min and it was sealed with a PTFE-lined cap, and then the tube was heated). After the reaction period, the reaction mixture was concentrated under vacuum and purification of the resulting reaction mixture by column chromatography on neutral alumina or silica gel (EtOAc/hexane) furnished the corresponding arylated carboxamide (see the corresponding Tables/Schemes for specific examples).

Pd(II)-Catalyzed Arylation of the Carboxamide 2b and Preparation of Compounds 5

A mixture of carboxamide 2b (0.2 mmol, 1 equiv), an appropriate aryl iodide (0.8–1.0 mmol, 4–5 equiv), Pd(OAc)₂ (4.5 mg, 10 mol%) and AgOAc (0.44 mmol, 2.2 equiv) in o-xylene (2 mL) was heated at 150 °C for 36–48 h in a 10 mL capacity sealed (pressure) tube (the pressure tube was flushed with nitrogen atmosphere for 2 min and it was sealed with a PTFE-lined cap, and then the tube was heated). After the reaction period, the reaction mixture was concentrated under vacuum and purification of the resulting reaction mixture by column chromatography on silica gel (EtOAc/hexane) furnished the corresponding arylated carboxamide (see the corresponding Tables/ Schemes for specific examples).

Pd(II)-Catalyzed Alkylation of Carboxamide 2a and Preparation of Compounds 10

A mixture of carboxamide 2a (0.14 mmol, 1 equiv), an appropriate alkyl iodide (0.56 mmol, 4 equiv), anhydrous K₂CO₃ (0.28 mmol, 2 equiv), NaOTf (0.42 mmol, 3 equiv), Pd(OAc)₂ (10 mol%, 3.4 mg), and t-AmylOH (2.0 mL) was added in a 10 mL capacity sealed (pressure) tube. The pressure tube was flushed with nitrogen atmosphere for 2 min, sealed with a PTFE-lined cap, and then the tube was heated at 125 °C for 48 h. After the reaction period, the reaction mixture was concentrated under vacuum and purification of the resulting reaction mixture by column chromatography on silica gel (EtOAc/hexane) furnished the corresponding alkylated carboxamide 10 (see the corresponding Tables/Schemes for specific examples).

Pd(II)-Catalyzed Alkylation of Carboxamide 2b and Preparation of Compounds 11

A mixture of 2b carboxamide (0.2 mmol, 1 equiv), an appropriate alkyl iodide (0.8 mmol, 4.0 equiv), anhydrous KOAc (0.4 mmol, 2 equiv), Pd(OAc)₂ (10 mol%, 4.5 mg), and 1,4-dioxane (2.0 mL) was added in a 10 mL capacity sealed (pressure) tube. The pressure tube was flushed with nitrogen atmosphere for 2 min, sealed with a PTFE-lined cap, and then heated at 130 °C for 36 h. After the reaction period, the reaction mixture was concentrated under vacuum and purification of the resulting reaction mixture by column chromatography on neutral alumina or silica gel (EtOAc/hexane) furnished the corresponding alkylated carboxamide 11 (see the corresponding Tables/Schemes for specific examples).

Pd(II)-Catalyzed Arylation of Carboxamides 2c and Preparation of Compounds 8a,b

A mixture of carboxamide 2c (0.2 mmol, 1 equiv), an appropriate boronic acid (0.25 mmol, 1.25 equiv), NFSI (0.25 mmol, 1.25 equiv), and Pd(OAc)₂ (10 mol%, 4.5 mg) was suspended in 1,2-DCE (2.0 mL) in a 10 mL capacity sealed (pressure) tube. The pressure tube was flushed with N₂ for 2 min and sealed with a PTFE-lined cap, and then the tube was heated at 90 °C for 24 h. After the reaction period, the mixture was filtered through a Celite® pad and washed with DCM (10–15 mL). The filtrate was concentrated, and the residue was purified by column chromatography on silica gel (EtOAc/hexane) to afford the corresponding arylated carboxamide 8 (see the corresponding Tables/Schemes for specific examples). The structures of compounds 8a,b were assigned based on reports of a similar compound prepared under Cu-catalyzed reaction involving aryliodonium salts as arylating reagent.[15k]

Directing Group Removal/Amide Hydrolysis and Preparation of Compound 13

A solution of NaOH (60 mg of NaOH) in EtOH/H₂O (10:1 v/v, 3.3 mL) containing an appropriate arylated carboxamide 5 (0.15 mmol) was heated at reflux for 24 h. The reaction mixture was then cooled to r.t. and the mixture was subjected to evaporation (to evaporate EtOH), then the solution was diluted with water (5 mL) and the product was extracted with EtOAc (3 × 5 mL). The organic layers were combined, dried with anhydrous MgSO₄ and concentrated. The residue was purified by column chromatography on silica gel (EtOAc/hexane) to afford the corresponding C–H arylated 1-aminopyrene derivative 13 (see the corresponding Tables/Schemes for specific examples).

N-(2-(Methylthio)phenyl)pyrene-1-carboxamide (2d)

By following the general procedure, compound 2d was obtained after purification by column chromatography on silica gel (EtOAc/hexane = 20:80) as a pale-yellow solid (521 mg, 71%, 2 mmol scale).

R_f = 0.5 (EtOAc/hexane = 20:80); mp 149–151 °C.

IR (DCM): 3275, 2925, 1682, 1513, 1436 cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 9.08 (s, 1 H), 8.79–8.72 (m, 2 H), 8.31 (d, J = 7.9 Hz, 1 H), 8.26–8.19 (m, 4 H), 8.15 (d, J = 8.9 Hz, 1 H), 8.09–8.05 (m, 2 H), 7.58 (d, J = 7.7 Hz, 1 H), 7.47 (t, J = 7.5 Hz, 1 H), 7.22–7.18 (m, 1 H), 2.40 (s, 3 H).

¹³C NMR (~101 MHz, CDCl₃): δ = 168.0, 138.7, 133.0, 133.0, 131.2, 130.7, 130.7, 129.1, 129.0, 129.0, 127.1, 126.5, 126.1, 126.0, 125.9, 124.9, 124.9, 124.7, 124.6, 124.4, 120.9, 19.1.

HRMS (ESI): m/z [M + Na]⁺ calcd for C₂₄H₁₇NNaOS: 390.0929; found: 390.0922.

2-(4-Acetylphenyl)-N-(quinolin-8-yl)pyrene-1-carboxamide (4a)

By following the general procedure, compound 4a was obtained after purification by column chromatography on silica gel (EtOAc/hexane = 20:80) as a pale-yellow solid (68 mg, 70%).

R_f = 0.4 (EtOAc/hexane = 20:80); mp 249–251 °C.

IR (DCM): 3338, 1679, 1519, 1483, 1264 cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 10.04 (s, 1 H), 8.99 (d, J = 7.5 Hz, 1 H), 8.55–8.54 (m, 1 H), 8.49 (d, J = 9.2 Hz, 1 H), 8.27–8.25 (m, 3 H), 8.19 (d, J = 9.0 Hz, 2 H), 8.14–8.06 (m, 3 H), 7.95 (d, J = 8.2 Hz, 2 H), 7.90 (d, J = 8.3 Hz, 2 H), 7.62 (t, J = 8.1 Hz, 1 H), 7.55 (d, J = 8.2 Hz, 1 H), 7.36 (dd, ¹ J = 8.2 Hz, ² J = 4.2 Hz, 1 H), 2.52 (s, 3 H).

¹³C NMR (~101 MHz, CDCl₃): δ = 196.8, 166.8, 147.1, 144.7, 137.4, 135.2, 135.0, 134.8, 133.3, 130.9, 130.3, 130.1, 129.7, 128.6, 128.3, 128.1, 127.8, 127.4, 126.8, 126.3, 126.0, 125.5, 125.0, 124.9, 124.9, 123.5, 123.1, 123.0, 121.1, 120.5, 115.7, 25.6.

HRMS (ESI): m/z [M + H]⁺ calcd for C₃₄H₂₃N₂O₂: 491.1760; found: 491.1779.

2-(4-Nitrophenyl)-N-(quinolin-8-yl)pyrene-1-carboxamide (4b)

By following the general procedure, compound 4b was obtained after purification by column chromatography on silica gel (EtOAc/hexane = 25:75) as a pale-yellow solid (84 mg, 86%).

R_f = 0.3 (EtOAc/hexane = 20:80); mp 237–239 °C.

IR (DCM): 2924, 1670, 1595, 1519, 1341 cm^–1.

¹H NMR (400 MHz, DMSO-d ₆): δ = 10.61 (s, 1 H), 8.73 (d, J = 4.0 Hz, 1 H), 8.61 (d, J = 7.5 Hz, 1 H), 8.47 (s, 1 H), 8.43–8.32 (m, 7 H), 8.27 (d, J = 8.6 Hz, 2 H), 8.17 (t, J = 7.6 Hz, 1 H), 8.05 (d, J = 8.6 Hz, 2 H), 7.76 (d, J = 8.2 Hz, 1 H), 7.66 (t, J = 7.8 Hz, 1 H), 7.56 (dd, ¹ J = 8.3 Hz, ² J = 4.2 Hz, 1 H).

¹³C NMR (~101 MHz, CDCl₃): δ = 167.5, 148.2, 147.6, 147.2, 138.3, 136.3, 134.8, 134.2, 132.0, 131.2, 130.8, 130.3, 129.6, 129.4, 128.9, 127.9, 127.3, 127.0, 126.8, 126.3, 126.1, 125.7, 124.5, 124.3, 124.1, 123.6, 123.6, 122.4, 121.7, 116.8.

HRMS (ESI): m/z [M + H]⁺ calcd for C₃₂H₂₀N₃O₃: 494.1505; found: 494.1520.

Methyl 4-(1-(Quinolin-8-ylcarbamoyl)pyren-2-yl)benzoate (4c)

By following the general procedure, compound 4c was obtained after purification by column chromatography on silica gel (EtOAc/hexane = 20:80) as a pale-yellow solid (58 mg, 58%).

R_f = 0.4 (EtOAc/hexane = 20:80); mp 160–162 °C.

IR (DCM): 3348, 2940, 1725, 1675, 1528 cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 10.03 (s, 1 H), 8.99 (d, J = 7.5 Hz, 1 H), 8.54 (d, J = 3.1 Hz, 1 H), 8.48 (d, J = 9.2 Hz, 1 H), 8.26–8.23 (m, 3 H), 8.17 (d, J = 9.0 Hz, 1 H), 8.12–8.03 (m, 5 H), 7.89 (d, J = 7.8 Hz, 1 H), 7.63–7.59 (m, 1 H), 7.53 (d, J = 8.2 Hz, 1 H), 7.34 (dd, ¹ J = 8.1 Hz, ² J = 4.1 Hz, 1 H), 3.86 (s, 3 H).

¹³C NMR (~101 MHz, CDCl₃): δ = 167.9, 166.9, 148.1, 145.6, 138.4, 136.2, 136.0, 134.4, 131.9, 131.3, 131.1, 130.7, 129.7, 129.5, 129.3, 129.1, 129.1, 128.8, 127.8, 127.3, 127.0, 126.5, 126.0, 125.9, 124.5, 124.2, 124.0, 122.2, 121.6, 116.9, 52.1.

HRMS (ESI): m/z [M + H]⁺ calcd for C₃₄H₂₃N₂O₃: 507.1709; found: 507.1695.

2-(4-Chlorophenyl)-N-(quinolin-8-yl)pyrene-1-carboxamide (4d)

By following the general procedure, compound 4d was obtained after purification by column chromatography on silica gel (EtOAc/hexane = 20:80) as a pale-yellow solid (51 mg, 53%).

R_f = 0.5 (EtOAc/hexane = 20:80); mp 237–239 °C.

IR (DCM): 3348, 2936, 1663, 1528, 1490 cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 10.02 (s, 1 H), 9.01–9.00 (m, 1 H), 8.56 (dd, ¹ J = 4.1 Hz, ² J = 1.4 Hz, 1 H), 8.47 (d, J = 9.2 Hz, 1 H), 8.27–8.24 (m, 3 H), 8.19–8.05 (m, 5 H), 7.74 (d, J = 8.4 Hz, 2 H), 7.64 (t, J = 7.8 Hz, 1 H), 7.58–7.56 (m, 1 H), 7.38 (dd, ¹ J = 8.3 Hz, ² J = 4.2 Hz, 1 H), 7.34 (d, J = 8.4 Hz, 2 H).

¹³C NMR (~101 MHz, CDCl₃): δ = 168.0, 148.1, 139.3, 138.4, 136.2, 135.9, 134.4, 133.7, 132.0, 131.4, 131.1, 130.7, 129.2, 129.0, 128.8, 128.6, 127.9, 127.3, 127.1, 126.5, 126.1, 126.0, 125.9, 124.6, 124.2, 123.9, 122.2, 121.6, 116.8.

HRMS (ESI): m/z [M + H]⁺ calcd for C₃₂H₂₀ClN₂O: 483.1264; found: 483.1252.

2-(2,3-Dihydrobenzo[b][1,4]dioxin-6-yl)-N-(quinolin-8-yl)pyrene-1-carboxamide (4e)

By following the general procedure, compound 4e was obtained after purification by column chromatography on silica gel (EtOAc/hexane = 20:80) as a pale-yellow solid (45 mg, 45%).

R_f = 0.4 (EtOAc/hexane = 20:80); mp 248–250 °C.

IR (DCM): 3338, 2924, 1667, 1516, 1323 cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 10.02 (s, 1 H), 9.04 (d, J = 7.6 Hz, 1 H), 8.59 (d, J = 4.0 Hz, 1 H), 8.48 (d, J = 9.2 Hz, 1 H), 8.26–8.23 (m, 3 H), 8.19–8.11 (m, 4 H), 8.05 (t, J = 7.6 Hz, 1 H), 7.64 (t, J = 7.9 Hz, 1 H), 7.55 (d, J = 8.2 Hz, 1 H), 7.39–7.34 (m, 2 H), 7.29–7.26 (m, 1 H), 6.81 (d, J = 8.3 Hz, 1 H), 4.17–4.16 (m, 4 H).

¹³C NMR (~101 MHz, CDCl₃): δ = 168.3, 148.0, 143.4, 143.2, 138.5, 136.7, 136.1, 134.7, 134.2, 131.9, 131.4, 131.1, 130.7, 129.0, 128.8, 128.8, 127.8, 127.4, 127.2, 126.3, 125.8, 125.7, 124.7, 124.3, 123.6, 122.6, 121.8, 121.5, 118.5, 117.2, 116.7, 64.3, 64.2.

HRMS (ESI): m/z [M + H]⁺ calcd for C₃₄H₂₃N₂O₃: 507.1709; found: 507.1724.

2-Phenyl-N-(quinolin-8-yl)pyrene-1-carboxamide (4f)

By following the general procedure, compound 4f was obtained after purification by column chromatography on silica gel (EtOAc/hexane = 20:80) as a pale-yellow solid (49 mg, 55%).

R_f = 0.5 (EtOAc/hexane = 20:80); mp 218–220 °C.

IR (DCM): 3342, 1667, 1519, 1483, 1325 cm^–1.

¹H NMR (500 MHz, CDCl₃): δ = 9.96 (s, 1 H), 8.97 (dd, ¹ J = 7.6 Hz, ² J = 1.0 Hz, 1 H), 8.52 (dd, ¹ J = 4.1 Hz, ² J = 1.4 Hz, 1 H), 8.47 (d, J = 9.3 Hz, 1 H), 8.27 (s, 1 H), 8.23 (t, J = 7.9 Hz, 2 H), 8.17–8.03 (m, 5 H), 7.83–7.77 (m, 2 H), 7.60–7.56 (m, 1 H), 7.50 (d, J = 8.3 Hz, 1 H), 7.34–7.31 (m, 3 H), 7.18 (t, J = 7.5 Hz, 1 H).

¹³C NMR (~126 MHz, CDCl₃): δ = 168.2, 148.0, 140.8, 138.4, 137.3, 136.1, 134.6, 131.9, 131.6, 131.2, 130.8, 129.4, 129.0, 128.9, 128.8, 128.4, 127.8, 127.5, 127.3, 127.2, 126.4, 126.3, 125.9, 125.8, 124.7, 124.4, 123.8, 121.8, 121.5, 116.6.

HRMS (ESI): m/z [M + H]⁺ calcd for C₃₂H₂₁N₂O: 449.1654; found: 449. 1649.

2-(4-Ethylphenyl)-N-(quinolin-8-yl)pyrene-1-carboxamide (4g)

By following the general procedure, compound 4g was obtained after purification by column chromatography on silica gel (EtOAc/hexane = 20:80) as a pale-yellow solid (67 mg, 71%).

R_f = 0.6 (EtOAc/hexane = 20:80); mp 205–207 °C.

IR (DCM): 3338, 1665, 1515, 1482, 1324 cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 9.99 (s, 1 H), 9.02 (d, J = 7.6 Hz, 1 H), 8.55–8.49 (m, 2 H), 8.30 (s, 1 H), 8.26–8.23 (m, 2 H), 8.19–8.05 (m, 5 H), 7.71 (d, J = 8.0 Hz, 2 H), 7.62 (t, J = 8.0 Hz, 1 H), 7.53 (d, J = 8.0 Hz, 1 H), 7.33 (dd, ¹ J = 8.4 Hz, ² J = 4.0 Hz, 1 H), 7.17 (d, J = 8.0 Hz, 2 H), 2.53 (q, J = 7.6 Hz, 2 H), 1.05 (t, J = 7.6 Hz, 3 H).

¹³C NMR (~101 MHz, CDCl₃): δ = 168.4, 147.9, 143.5, 138.4, 138.1, 137.3, 135.9, 134.7, 131.9, 131.5, 131.1, 130.7, 129.4, 129.0, 128.8, 128.8, 128.0, 127.8, 127.3, 127.1, 126.4, 126.2, 125.8, 125.7, 124.7, 124.3, 123.6, 121.8, 121.4, 116.6, 28.5, 15.4.

HRMS (ESI): m/z [M + H]⁺ calcd for C₃₄H₂₅N₂O: 477.1967; found: 477.1982.

2-(4-Isopropylphenyl)-N-(quinolin-8-yl)pyrene-1-carboxamide (4h)

By following the general procedure, compound 4h was obtained after purification by column chromatography on silica gel (EtOAc/hexane = 20:80) as a pale-yellow solid (65 mg, 66%).

R_f = 0.5 (EtOAc/hexane = 20:80); mp 160–162 °C.

IR (DCM): 3337, 2959, 1662, 1519, 1481 cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 9.99 (s, 1 H), 9.03 (dd, ¹ J = 7.6 Hz, ² J = 0.9 Hz, 1 H), 8.55–8.51 (m, 2 H), 8.28 (s, 1 H), 8.24–8.22 (m, 2 H), 8.18–8.03 (m, 5 H), 7.74 (d, J = 8.1 Hz, 1 H), 7.60 (t, J = 8.0 Hz, 1 H), 7.49 (dd, ¹ J = 8.3 Hz, ² J = 0.9 Hz, 1 H), 7.32–7.28 (m, 1 H), 7.19 (d, J = 8.1 Hz, 2 H), 2.80–2.72 (m, 1 H), 1.05 (d, J = 6.9 Hz, 6 H).

¹³C NMR (~101 MHz, CDCl₃): δ = 168.3, 148.0, 147.8, 138.3, 138.2, 137.3, 135.8, 134.7, 131.9, 131.4, 131.0, 130.6, 129.4, 128.9, 128.8, 128.7, 127.6, 127.2, 127.1, 126.4, 126.3, 126.2, 125.7, 125.6, 124.7, 124.3, 123.6, 121.7, 121.3, 116.4, 33.6, 23.7.

HRMS (ESI): m/z [M + H]⁺ calcd for C₃₅H₂₇N₂O: 491.2123; found: 491.2142.

N-(Quinolin-8-yl)-2-(p-tolyl)pyrene-1-carboxamide (4i)

By following the general procedure, compound 4i was obtained after purification by column chromatography on silica gel (EtOAc/hexane = 20:80) as a pale-yellow solid (54 mg, 58%).

R_f = 0.5 (EtOAc/hexane = 20:80); mp 195–197 °C.

IR (DCM): 3355, 3052, 1690, 1536, 1321 cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 10.04 (s, 1 H), 9.04 (d, J = 7.5 Hz, 1 H), 8.54 (dd, ¹ J = 4.0 Hz, ² J = 1.4 Hz, 1 H), 8.48 (d, J = 9.2 Hz, 1 H), 8.27–8.21 (m, 3 H), 8.16–8.03 (m, 5 H), 7.72 (d, J = 7.9 Hz, 2 H), 7.62 (t, J = 8.1 Hz, 1 H), 7.51 (d, J = 8.2 Hz, 1 H), 7.32 (dd, ¹ J = 8.2 Hz, ² J = 4.2 Hz, 1 H), 7.18 (d, J = 7.8 Hz, 2 H), 2.26 (s, 3 H).

¹³C NMR (~101 MHz, CDCl₃): δ = 168.4, 148.0, 138.4, 137.9, 137.2, 136.0, 134.7, 131.9, 131.5, 131.1, 130.7, 129.3, 129.2, 128.0, 128.8, 128.7, 127.8, 127.3, 127.2, 126.4, 126.3, 125.8, 125.7, 124.7, 124.3, 123.6, 121.9, 121.5, 116.7, 21.1.

HRMS (ESI): m/z [M + H]⁺ calcd for C₃₃H₂₃N₂O: 463.1810; found: 463.1791.

2-(4-Methoxyphenyl)-N-(quinolin-8-yl)pyrene-1-carboxamide (4j)

By following the general procedure, compound 4j was obtained after purification by column chromatography on silica gel (EtOAc/hexane = 25:75) as a pale-yellow solid (64 mg, 67%).

R_f = 0.4 (EtOAc/hexane = 20:80); mp 178–180 °C.

IR (DCM): 3336, 2932, 1682, 1521, 1321 cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 10.02 (s, 1 H), 9.05 (d, J = 7.5 Hz, 1 H), 8.55–8.54 (m, 1 H), 8.48 (d, J = 9.2 Hz, 1 H), 8.26–8.22 (m, 3 H), 8.16 (d, J = 9.1 Hz, 2 H), 8.12–8.03 (m, 3 H), 7.75 (d, J = 7.7 Hz, 2 H), 7.62 (t, J = 7.9 Hz, 1 H), 7.53 (d, J = 8.2 Hz, 1 H), 7.33 (dd, ¹ J = 7.8 Hz, ² J = 4.0 Hz, 1 H), 6.91 (d, J = 7.8 Hz, 2 H), 3.71 (s, 3 H).

¹³C NMR (~101 MHz, CDCl₃): δ = 168.5, 159.1, 148.0, 138.4, 136.9, 136.1, 134.7, 133.2, 131.9, 131.5, 131.1, 130.7, 130.6, 129.0, 128.8, 128.8, 127.8, 127.3, 127.2, 126.4, 126.3, 125.8, 125.7, 124.7, 124.3, 123.5, 121.9, 121.5, 116.6, 113.9, 55.2.

HRMS (ESI): m/z [M + H]⁺ calcd for C₃₃H₂₃N₂O₂: 479.1760; found: 479.1775.

2-(3-Methoxyphenyl)-N-(quinolin-8-yl)pyrene-1-carboxamide (4k)

By following the general procedure, compound 4k was obtained after purification by column chromatography on silica gel (EtOAc/hexane = 20:80) as a pale-yellow solid (73 mg, 77%).

R_f = 0.4 (EtOAc/hexane = 20:80); mp 201–203 °C.

IR (CH₂Cl₂): 3337, 1665, 1516, 1482, 1324 cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 10.04 (s, 1 H), 9.03 (d, J = 7.6 Hz, 1 H), 8.55 (d, J = 3.9 Hz, 1 H), 8.50 (d, J = 9.2 Hz, 1 H), 8.29 (s, 1 H), 8.23 (d, J = 7.6 Hz, 2 H), 8.18–8.14 (m, 2 H), 8.11–8.03 (m, 3 H), 7.61 (t, J = 7.9 Hz, 1 H), 7.52 (d, J = 8.3 Hz, 1 H), 7.41–7.39 (m, 2 H), 7.33 (dd, ¹ J = 8.0 Hz, ² J = 4.0 Hz, 1 H), 7.26–7.24 (m, 1 H), 6.77 (d, J = 7.9 Hz, 1 H), 3.75 (s, 3 H).

¹³C NMR (~101 MHz, CDCl₃): δ = 168.3, 159.5, 148.0, 142.2, 138.4, 137.1, 136.1, 134.7, 131.9, 131.5, 131.1, 130.7, 129.4, 129.1, 128.9, 128.8, 127.8, 127.3, 127.1, 126.3, 126.2, 125.9, 125.8, 124.7, 124.3, 123.8, 122.0, 121.9, 121.5, 116.7, 114.5, 113.9, 55.3.

HRMS (ESI): m/z [M + H]⁺ calcd for C₃₃H₂₃N₂O₂: 479.1760; found: 479.1780.

N-(Quinolin-8-yl)-2-(m-tolyl)pyrene-1-carboxamide (4l)

By following the general procedure, compound 4l was obtained after purification by column chromatography on silica gel (EtOAc/hexane = 20:80) as a pale-yellow solid (57 mg, 84%, 0.15 mmol scale).

R_f = 0.5 (EtOAc/hexane = 20:80); mp 186–188 °C.

IR (DCM): 3333, 1667, 1519, 1483, 1325 cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 10.01 (s, 1 H), 9.01 (d, J = 7.6 Hz, 1 H), 8.56 (d, J = 4.0 Hz, 1 H), 8.51 (d, J = 9.2 Hz, 1 H), 8.28 (s, 1 H), 8.26–8.23 (m, 2 H), 8.17 (d, J = 9.2 Hz, 2 H), 8.13–8.04 (m, 3 H), 7.63–7.59 (m, 3 H), 7.52 (d, J = 8.2 Hz, 1 H), 7.34 (dd, ¹ J = 8.2 Hz, ² J = 4.2 Hz, 1 H), 7.22 (t, J = 7.6 Hz, 1 H), 7.01 (d, J = 7.6 Hz, 1 H), 2.30 (s, 3 H).

¹³C NMR (~101 MHz, CDCl₃): δ = 168.3, 148.0, 140.7, 138.4, 137.9, 137.5, 136.1, 134.7, 131.9, 131.6, 131.1, 130.7, 130.2, 129.0, 128.8, 128.7, 128.2, 128.2, 127.8, 127.3, 127.2, 126.5, 126.3, 125.8, 125.7, 124.7, 124.4, 123.7, 121.8, 121.5, 116.6, 21.4.

HRMS (ESI): m/z [M + H]⁺ calcd for C₃₃H₂₃N₂O: 463.1810; found: 463.1827.

2-(3-Chlorophenyl)-N-(quinolin-8-yl)pyrene-1-carboxamide (4m)

By following the general procedure, compound 4m was obtained after purification by column chromatography on silica gel (EtOAc/hexane = 20:80) as a pale-yellow solid (71 mg, 74%).

R_f = 0.5 (EtOAc/hexane = 20:80); mp 218–220 °C.

IR (DCM): 3334, 2923, 1668, 1519, 1483 cm^–1.

¹H NMR (500 MHz, CDCl₃): δ = 9.96 (s, 1 H), 8.95 (dd, ¹ J = 7.6 Hz, ² J = 1.0 Hz, 1 H), 8.57 (dd, ¹ J = 4.1 Hz, ² J = 1.6 Hz, 1 H), 8.48 (d, J = 9.2 Hz, 1 H), 8.26–8.23 (m, 3 H), 8.19–8.16 (m, 2 H), 8.12–8.04 (m, 3 H), 7.80 (t, J = 1.8 Hz, 1 H), 7.63–7.58 (m, 2 H), 7.52 (dd, ¹ J = 8.4 Hz, ² J = 1.1 Hz, 1 H), 7.35 (dd, ¹ J = 8.3 Hz, ² J = 4.2 Hz, 1 H), 7.18 (t, J = 7.7 Hz, 1 H), 7.14–7.12 (m, 1 H).

¹³C NMR (~126 MHz, CDCl₃): δ = 167.8, 148.2, 142.6, 138.4, 136.1, 135.8, 134.5, 134.3, 132.0, 131.4, 131.2, 130.8, 129.6, 129.5, 129.3, 129.1, 128.9, 127.8, 127.6, 127.5, 127.3, 127.1, 126.5, 126.0, 126.0, 125.9, 124.7, 124.3, 124.0, 122.0, 121.6, 116.7.

HRMS (ESI): m/z [M + H]⁺ calcd for C₃₂H₂₀ClN₂O: 483.1264; found: 483.1261.

2-(3-Fluorophenyl)-N-(quinolin-8-yl)pyrene-1-carboxamide (4n)

By following the general procedure, compound 4n was obtained after purification by column chromatography on silica gel (EtOAc/hexane = 20:80) as a pale-yellow solid (61 mg, 66%).

R_f = 0.5 (EtOAc/hexane = 20:80); mp 217–219 °C.

IR (DCM): 3342, 1667, 1519, 1483, 1423 cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 10.03 (s, 1 H), 9.00 (d, J = 7.6 Hz, 1 H), 8.54 (d, J = 3.9 Hz, 1 H), 8.47 (d, J = 9.2 Hz, 1 H), 8.21–8.10 (m, 5 H), 8.06–8.01 (m, 3 H), 7.62–7.54 (m, 3 H), 7.50 (d, J = 8.3 Hz, 1 H), 7.33–7.25 (m, 2 H), 6.91 (t, J = 8.1 Hz, 1 H).

¹³C NMR (~101 MHz, CDCl₃): δ = 167.9, 162.7 (d, J _C–F = 245 Hz), 148.1, 143.0 (d, J _C–F = 5.3 Hz), 138.3, 136.1, 135.8 (d, J _C–F = 1.5 Hz), 134.5, 131.9, 131.3, 131.1, 130.7, 129.9 (d, J _C–F = 8.4 Hz), 129.2, 129.0, 128.8, 127.8, 127.3, 127.0, 126.5, 126.0, 125.8, 125.3 (d, J _C–F = 2.5 Hz), 124.6, 124.1, 123.9, 122.1, 121.6, 116.7, 116.5 (d, J _C–F = 22.0 Hz), 114.4 (d, J _C–F = 21.0 Hz).

HRMS (ESI): m/z [M + H]⁺ calcd for C₃₂H₂₀FN₂O: 467.1560; found: 467.1574.

2-(5-Bromopyridin-2-yl)-N-(quinolin-8-yl)pyrene-1-carboxamide (4o)

By following the general procedure, compound 4o was obtained after purification by column chromatography on silica gel (EtOAc/hexane = 20:80) as a pale-yellow solid (61 mg, 58%).

R_f = 0.4 (EtOAc/hexane = 20:80); mp 115–117 °C.

IR (DCM): 3338, 2924, 1667, 1519, 1483 cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 10.13 (s, 1 H), 9.05 (d, J = 7.3 Hz, 1 H), 8.70 (d, J = 1.8 Hz, 1 H), 8.57–8.51 (m, 3 H), 8.27–8.06 (m, 7 H), 7.84 (d, J = 8.4 Hz, 1 H), 7.77 (dd, ¹ J = 8.4 Hz, ² J = 2.2 Hz, 1 H), 7.67 (t, J = 8.0 Hz, 1 H), 7.59 (d, J = 7.7 Hz, 1 H), 7.38 (dd, ¹ J = 8.3 Hz, ² J = 4.2 Hz, 1 H).

¹³C NMR (~101 MHz, CDCl₃): δ = 168.3, 156.6, 150.6, 148.2, 139.0, 138.5, 136.1, 134.7, 134.4, 132.0, 131.3, 131.1, 130.8, 129.2, 129.0, 127.9, 127.3, 127.3, 126.7, 126.0, 125.9, 125.7, 125.2, 124.6, 124.6, 124.1, 122.1, 121.6, 119.8, 116.9.

HRMS (ESI): m/z [M + H]⁺ calcd for C₃₁H₁₉BrN₃O: 528.0711; found: 528.0685.

2-(6-Chloropyridin-3-yl)-N-(quinolin-8-yl)pyrene-1-carboxamide (4p)

By following the general procedure, compound 4p was obtained after purification by column chromatography on silica gel (EtOAc/hexane = 20:80) as a pale-yellow solid (23 mg, 48%, 0.1 mmol scale).

R_f = 0.4 (EtOAc/hexane = 20:80); mp 135–137 °C.

IR (DCM): 3344, 2917, 1682, 1536, 1332 cm^–1.

¹H NMR (400 MHz, DMSO-d ₆): δ = 10.64 (s, 1 H), 8.78 (d, J = 2.3 Hz, 1 H), 8.74 (dd, ¹ J = 4.2 Hz, ² J = 1.5 Hz, 1 H), 8.62–8.60 (m, 1 H), 8.47 (s, 1 H), 8.43–8.30 (m, 7 H), 8.23 (dd, ¹ J = 8.2 Hz, ² J = 2.5 Hz, 1 H), 8.16 (t, J = 7.6 Hz, 1 H), 7.79–7.77 (m, 1 H), 7.69–7.65 (m, 1 H), 7.60–7.57 (m, 2 H).

¹³C NMR (~101 MHz, CDCl₃): δ = 167.4, 150.7, 149.7, 148.3, 139.5, 138.3, 136.3, 135.5, 134.1, 132.1, 132.0, 131.4, 131.2, 130.7, 129.6, 129.4, 129.0, 127.9, 127.3, 126.9, 126.8, 126.3, 126.1, 125.8, 124.4, 124.2, 124.1, 123.8, 122.5, 121.7, 117.1.

HRMS (ESI): m/z [M + H]⁺ calcd for C₃₁H₁₉ClN₃O: 484.1217; found: 484.1205.

N-(Quinolin-8-yl)-2-(thiophen-2-yl)pyrene-1-carboxamide (4q)

By following the general procedure, compound 4q was obtained after purification by column chromatography on silica gel (EtOAc/hexane = 20:80) as a pale-yellow solid (48 mg, 54%).

R_f = 0.4 (EtOAc/hexane = 20:80); mp 221–223 °C.

IR (DCM): 3332, 2921, 1667, 1525, 1467 cm^–1.

¹H NMR (400 MHz, DMSO-d ₆): δ = 10.54 (s, 1 H), 8.83 (d, J = 7.4 Hz, 1 H), 8.72 (d, J = 4.0 Hz, 1 H), 8.56 (s, 1 H), 8.43–8.25 (m, 7 H), 8.16–8.15 (m, 1 H), 7.79 (d, J = 8.2 Hz, 1 H), 7.74–7.72 (m, 1 H), 7.63–7.56 (m, 3 H), 7.12–7.10 (m, 1 H).

¹³C NMR (~101 MHz, DMSO-d ₆): δ = 167.8, 149.6, 141.8, 138.8, 137.1, 134.7, 131.8, 131.4, 131.2, 130.6, 129.8, 129.5, 129.3, 128.5, 128.4, 128.4, 128.2, 127.8, 127.6, 127.5, 127.4, 126.8, 126.5, 126.3, 124.6, 123.8, 1235, 123.2, 122.7, 118.1.

HRMS (ESI): m/z [M + H]⁺ calcd for C₃₀H₁₉N₂OS: 455.1218; found: 455.1199.

N-(10-(3-Methoxyphenyl)pyren-1-yl)picolinamide (5a)

By following the general procedure, compound 5a was obtained after purification by column chromatography on silica gel (EtOAc/hexane = 25:75) as a brown solid (61 mg, 71%).

R_f = 0.3 (EtOAc/hexane = 20:80); mp 167–169 °C.

IR (DCM): 3475, 3352, 1667, 1602, 1517 cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 9.86 (s, 1 H), 8.69 (d, J = 8.3 Hz, 1 H), 8.32–8.28 (m, 2 H), 8.18 (d, J = 7.6 Hz, 2 H), 8.12–8.06 (m, 3 H), 8.04–7.98 (m, 1 H), 7.94 (s, 1 H), 7.82 (t, J = 7.6 Hz, 1 H), 7.40–7.37 (m, 1 H), 7.15–7.11 (m, 3 H), 6.55–6.54 (m, 1 H), 3.74 (s, 3 H).

¹³C NMR (~101 MHz, CDCl₃): δ = 162.2, 159.6, 149.8, 147.4, 144.3, 137.1, 136.5, 131.3, 131.3, 130.3, 129.4, 129.4, 127.7, 126.6, 126.4, 126.3, 126.1, 126.0, 125.4, 124.8, 124.3, 124.0, 122.0, 121.8, 121.4, 113.7, 113.2, 55.1.

HRMS (ESI): m/z [M + H]⁺ calcd for C₂₉H₂₁N₂O₂: 429.1603; found: 429.1593.

N-(10-(m-Tolyl)pyren-1-yl)picolinamide (5b)

By following the general procedure, compound 5b was obtained after purification by column chromatography on silica gel (EtOAc/hexane = 20:80) as a brown solid (46 mg, 57%).

R_f = 0.5 (EtOAc/hexane = 20:80); mp 167–169 °C.

IR (DCM): 3325, 3040, 1690, 1517, 1478 cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 9.80 (s, 1 H), 8.71 (d, J = 8.4 Hz, 1 H), 8.31–8.26 (m, 2 H), 8.20–8.18 (m, 2 H), 8.12–8.05 (m, 3 H), 8.01 (t, J = 7.6 Hz, 1 H), 7.93 (s, 1 H), 7.81 (td, ¹ J = 7.7 Hz, ² J = 1.1 Hz, 1 H), 7.39–7.36 (m, 3 H), 7.14 (t, J = 7.6 Hz, 1 H), 6.81 (d, J = 7.6 Hz, 1 H), 2.24 (s, 3 H).

¹³C NMR (~101 MHz, CDCl₃): δ = 162.1, 149.8, 147.3, 142.9, 137.9, 137.0, 136.8, 131.4, 131.3, 130.4, 129.7, 129.4, 128.3, 127.8, 127.6, 126.6, 126.5, 126.3, 126.1, 126.0, 125.9, 125.3, 124.7, 124.3, 124.0, 122.1, 121.9, 21.3.

HRMS (ESI): m/z [M + H]⁺ calcd for C₂₉H₂₁N₂O: 413.1654; found: 413.1639.

N-(10-(3-Fluorophenyl)pyren-1-yl)picolinamide (5c)

By following the general procedure, compound 5b was obtained after purification by column chromatography on silica gel (EtOAc/hexane = 20:80) as a brown solid (47 mg, 57%).

R_f = 0.5 (EtOAc/hexane = 20:80); mp 195–197 °C.

IR (DCM): 3328, 2921, 1671, 1521, 1486 cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 9.80 (s, 1 H), 8.70 (d, J = 8.4 Hz, 1 H), 8.35–8.34 (m, 1 H), 8.30 (d, J = 8.4 Hz, 1 H), 8.22–8.18 (m, 2 H), 8.13–8.00 (m, 4 H), 7.92 (s, 1 H), 7.84 (td, ¹ J = 7.7 Hz, ² J = 1.7 Hz, 1 H), 7.43–7.36 (m, 2 H), 7.25–7.23 (m, 1 H), 7.16–7.10 (m, 1 H), 6.73–6.68 (m, 1 H).

¹³C NMR (~101 MHz, CDCl₃): δ = 162.9 (d, J _C–F = 245.2 Hz), 162.0, 149.6, 147.4, 145.2 (d, J _C–F = 7.8 Hz), 137.2, 135.2 (d, J _C–F = 1.7 Hz), 131.6, 131.3, 131.2, 130.1, 129.7 (d, J _C–F = 8.5 Hz), 129.4, 127.8, 126.6, 126.4, 126.3, 126.2, 125.7, 125.1, 125.0 (d, J _C–F = 2.8 Hz), 124.9, 124.4, 123.9, 122.0, 121.8, 115.9 (d, J _C–F = 21.8 Hz), 113.5 (J _C–F = 20.8 Hz).

HRMS (ESI): m/z [M + H]⁺ calcd for C₂₈H₁₈FN₂O: 417.1403; found: 417.1393.

Ethyl 3-(3-(Picolinamido)pyren-4-yl)benzoate (5d)

By following the general procedure, compound 5d was obtained after purification by column chromatography on silica gel (EtOAc/hexane = 20:80) as a brown solid (59 mg, 63%).

R_f = 0.4 (EtOAc/hexane = 20:80); mp 157–159 °C.

IR (DCM): 3328, 2921, 1671, 1521, 1486 cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 9.72 (s, 1 H), 8.68 (d, J = 8.4 Hz, 1 H), 8.36–8.31 (m, 2 H), 8.23 (d, J = 7.3 Hz, 1 H), 8.18–8.09 (m, 5 H), 8.04 (t, J = 7.6 Hz, 1 H), 7.96 (s, 1 H), 7.81 (td, ¹ J = 7.7 Hz, ² J = 1.6 Hz, 1 H), 7.71 (d, J = 7.8 Hz, 1 H), 7.66–7.64 (m, 1 H), 7.39–7.36 (m, 1 H), 7.24 (t, J = 7.7 Hz, 1 H), 4.45–4.39 (m, 2 H), 1.43 (t, J = 7.1 Hz, 3 H).

¹³C NMR (~101 MHz, CDCl₃): δ = 166.5, 161.8, 149.5, 147.4, 143.2, 137.1, 135.6, 133.6, 131.9, 131.3, 131.0, 130.7, 130.2, 129.5, 129.5, 128.1, 128.1, 127.7, 126.7, 126.4, 126.3, 126.2, 125.7, 124.9, 124.4, 124.1, 121.9, 121.9, 61.01, 14.5.

HRMS (ESI): m/z [M + H]⁺ calcd for C₃₁H₂₃N₂O₃: 471.1709; found: 471.1716.

N-(10-(3-Acetylphenyl)pyren-1-yl)picolinamide (5e)

By following the general procedure, compound 5e was obtained after purification by column chromatography on silica gel (EtOAc/hexane = 20:80) as a brown solid (52 mg, 59%).

R_f = 0.3 (EtOAc/hexane = 20:80); mp 168–170 °C.

IR (DCM): 3440, 1686, 1602, 1513, 1248 cm^–1.

¹H NMR (400 MHz, DMSO-d ₆): δ = 10.03 (s, 1 H), 8.42 (d, J = 8.3 Hz, 1 H), 8.36–8.21 (m, 6 H), 8.11 (t, J = 7.6 Hz, 1 H), 8.01 (s, 1 H), 7.99 (s, 1 H), 7.93–7.86 (m, 2 H), 7.67 (d, J = 7.5 Hz, 1 H), 7.56–7.53 (m, 1 H), 7.41 (d, J = 7.9 Hz, 1 H), 7.28 (t, J = 7.7 Hz, 1 H), 2.46 (s, 3 H).

¹³C NMR (~101 MHz, CDCl₃): δ = 197.9, 161.8, 149.3, 147.4, 143.4, 137.3, 136.9, 135.5, 133.4, 131.9, 131.2, 130.8, 130.1, 129.6, 129.0, 128.5, 127.7, 126.8, 126.5, 126.4, 126.3, 126.3, 126.2, 125.7, 125.0, 124.6, 124.3, 122.2, 121.8, 26.7.

HRMS (ESI): m/z [M + H]⁺ calcd for C₃₀H₂₁N₂O₂: 441.1603; found: 441.1589.

N-(10-(4-Methoxyphenyl)pyren-1-yl)picolinamide (5f)

By following the general procedure, compound 5f was obtained after purification by column chromatography on silica gel (EtOAc/hexane = 20:80) as a brown solid (42 mg, 50%).

R_f = 0.4 (EtOAc/hexane = 20:80); mp 171–173 °C.

IR (CH₂Cl₂): 3396, 2951, 1678, 1556, 1514 cm^–1.

¹H NMR (500 MHz, CDCl₃): δ = 9.98 (s, 1 H), 8.80 (d, J = 8.4 Hz, 1 H), 8.32–8.29 (m, 2 H), 8.22–8.19 (m, 2 H), 8.15–8.01 (m, 4 H), 7.95 (s, 1 H), 7.87–7.83 (m, 1 H), 7.51 (d, J = 8.8 Hz, 2 H), 7.41–7.38 (m, 1 H), 6.81 (d, J = 8.4 Hz, 2 H), 3.63 (s, 3 H).

¹³C NMR (~101 MHz, CDCl₃): δ = 162.0, 159.0, 150.0, 147.5, 137.0, 136.2, 135.2, 131.6, 131.5, 131.3, 130.4, 130.1, 129.2, 127.7, 126.5, 126.5, 126.3, 126.1, 125.8, 125.2, 124.6, 124.3, 123.4, 121.9, 121.7, 113.8, 55.0.

HRMS (ESI): m/z [M + H]⁺ calcd for C₂₉H₂₁N₂O₂: 429.1603; found: 429.1588.

N-(10-(p-Tolyl)pyren-1-yl)picolinamide (5g)

By following the general procedure, compound 5g was obtained after purification by column chromatography on silica gel (EtOAc/hexane = 20:80) as a brown solid (51 mg, 62%).

R_f = 0.5 (EtOAc/hexane = 20:80); mp 158–160 °C.

IR (DCM): 3348, 3048, 1682, 1521, 1325 cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 9.88 (s, 1 H), 8.75 (d, J = 8.4 Hz, 1 H), 8.31–8.26 (m, 2 H), 8.19 (d, J = 7.7 Hz, 2 H), 8.13–8.05 (m, 3 H), 8.01 (t, J = 7.6 Hz, 1 H), 7.93 (s, 1 H), 7.8 (td, ¹ J = 7.7 Hz, ² J = 1.6 Hz, 1 H), 7.46 (d, J = 8.0 Hz, 2 H), 7.38–7.35 (m, 1 H), 7.06 (d, J = 7.8 Hz, 2 H), 2.13 (s, 3 H).

¹³C NMR (~101 MHz, CDCl₃): δ = 162.0, 150.0, 147.4, 140.0, 137.0, 136.7, 136.6, 131.5, 131.3, 130.4, 129.3, 129.0, 128.9, 127.8, 126.5, 126.3, 126.1, 125.8, 125.3, 124.7, 124.3, 123.6, 121.9, 21.1.

HRMS (ESI): m/z [M + H]⁺ calcd for C₂₉H₂₁N₂O: 413.1654; found: 413.1669.

N-(10-(4-Ethoxyphenyl)pyren-1-yl)picolinamide (5h)

By following the general procedure, compound 5h was obtained after purification by column chromatography on silica gel (EtOAc/hexane = 20:80) as a brown solid (53 mg, 61%).

R_f = 0.4 (EtOAc/hexane = 20:80); mp 148–150 °C.

IR (DCM): 3296, 2926, 1674, 1511, 1495 cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 9.97 (s, 1 H), 8.79 (d, J = 8.4 Hz, 1 H), 8.30–8.29 (m, 2 H), 8.19–8.17 (m, 2 H), 8.12–7.99 (m, 4 H), 7.93 (s, 1 H), 7.84– 8.0 (m, 1 H), 7.47 (d, J = 8.6 Hz, 2 H), 7.38–7.35 (m, 1 H), 6.77 (d, J = 8.6 Hz, 2 H), 3.78 (q, J = 7.0 Hz, 2 H), 1.35 (t, J = 7.0 Hz, 3 H).

¹³C NMR (~101 MHz, CDCl₃): δ = 162.0, 158.4, 150.0, 147.5, 137.0, 136.3, 135.0, 131.6, 131.5, 131.3, 130.4, 130.1, 129.2, 127.8, 126.5, 126.5, 126.3, 126.1, 125.7, 125.2, 124.6, 124.3, 123.3, 121.9, 121.7, 114.2, 63.1, 14.9.

HRMS (ESI): m/z [M + H]⁺ calcd for C₃₀H₂₃N₂O₂: 443.1760; found: 443.1775.

N-(10-Phenylpyren-1-yl)picolinamide (5i)

By following the general procedure, compound 5i was obtained after purification by column chromatography on silica gel (EtOAc/hexane = 20:80) as a brown solid (48 mg, 60%).

R_f = 0.5 (EtOAc/hexane = 20:80); mp 167–169 °C.

IR (DCM): 3347, 2923, 1678, 1511, 839 cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 9.85 (s, 1 H), 8.75 (d, J = 8.4 Hz, 1 H), 8.31 (d, J = 8.4 Hz, 1 H), 8.25 (d, J = 4.6 Hz, 1 H), 8.22–8.00 (m, 6 H), 7.94 (s, 1 H), 7.81 (td, ¹ J = 7.6 Hz, ² J = 1.4 Hz, 1 H), 7.57 (d, J = 7.3 Hz, 2 H), 7.38 –7.35 (m, 1 H), 7.28–7.24 (m, 2 H), 7.04 (t, J = 7.5 Hz, 1 H).

¹³C NMR (~101 MHz, CDCl₃): δ = 162.0, 149.8, 147.5, 142.9, 137.0, 136.6, 131.7, 131.5, 131.3, 130.3, 129.3, 129.0, 128.3, 127.7, 126.9, 126.5, 126.5, 126.3, 126.1, 125.9, 125.4, 124.8, 124.3, 123.6, 121.9, 121.7.

HRMS (ESI): m/z [M + H]⁺ calcd for C₂₈H₁₉N₂O: 399.1497; found: 399.1511.

N-(10-(4-Acetylphenyl)pyren-1-yl)picolinamide (5j)

By following the general procedure, 5j was obtained after purification by column chromatography on silica gel (EtOAc/hexane = 25:75) as a brown solid (54 mg, 61%).

R_f = 0.3 (EtOAc/hexane = 20:80); mp 158–160 °C.

IR (DCM): 3452, 3344, 1682, 1605, 1517 cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 9.54 (s, 1 H), 8.56 (d, J = 8.3 Hz, 1 H), 8.25 (d, J = 8.3 Hz, 1 H), 8.18–8.13 (m, 3 H), 8.09–8.04 (m, 3 H), 8.00–7.98 (m, 1 H), 7.87 (s, 1 H), 7.79–7.76 (m, 3 H), 7.57 (d, J = 7.8 Hz, 2 H), 7.30–7.28 (m, 1 H), 2.36 (s, 1 H).

¹³C NMR (~101 MHz, CDCl₃): δ = 197.3, 161.9, 149.5, 148.0, 147.4, 137.1, 135.5, 135.3, 131.5, 131.2, 130.8, 130.0, 129.6, 129.1, 128.3, 127.7, 126.7, 126.5, 126.3, 126.3, 126.1, 125.8, 125.1, 124.5, 124.3, 122.0, 121.9, 26.4.

HRMS (ESI): m/z [M + H]⁺ calcd for C₃₀H₂₁N₂O₂: 441.1603; found: 441.1624.

Methyl 4-(3-(Picolinamido)pyren-4-yl)benzoate (5k)

By following the general procedure, compound 5k was obtained after purification by column chromatography on silica gel (EtOAc/hexane = 25: 75) as a brown solid (58 mg, 64%).

R_f = 0.3 (EtOAc/hexane = 20:80); mp 125–127 °C.

IR (DCM): 3500, 1716, 1678, 1512, 1434 cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 9.59 (s, 1 H), 8.61 (d, J = 8.3 Hz, 1 H), 8.29 (d, J = 8.4 Hz, 1 H), 8.22–8.20 (m, 2 H), 8.15–8.05 (m, 4 H), 8.02 (t, J = 7.6 Hz, 1 H), 7.92 (s, 1 H), 7.88 (d, J = 8.3 Hz, 2 H), 7.79 (td, ¹ J = 7.6 Hz, ² J = 1.6 Hz, 1 H), 7.60 (d, J = 8.2 Hz, 2 H), 7.32–7.28 (m, 1 H), 3.87 (s, 3 H).

¹³C NMR (~101 MHz, CDCl₃): δ = 166.6, 162.0, 149.5, 147.8, 147.5, 137.1, 135.7, 131.5, 131.3, 131.0, 130.1, 129.6, 129.5, 128.9, 128.5, 127.7, 126.7, 126.4, 126.4, 126.3, 125.9, 125.8, 125.1, 124.4, 124.4, 122.0, 121.9, 51.9.

HRMS (ESI): m/z [M + H]⁺ calcd for C₃₀H₂₁N₂O₃: 457.1552; found: 457.1535.

N-(10-(4-Cyanophenyl)pyren-1-yl)picolinamide (5l)

By following the general procedure, compound 5l was obtained after purification by column chromatography on silica gel (EtOAc/hexane = 20:80) as a brown solid (47 mg, 56%).

R_f = 0.4 (EtOAc/hexane = 20:80); mp 213–215 °C.

IR (DCM): 3322, 2924, 2226, 1679, 1513 cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 9.54 (s, 1 H), 8.56 (d, J = 8.3 Hz, 1 H), 8.35–8.32 (m, 2 H), 8.26 (d, J = 7.5 Hz, 1 H), 8.19–8.10 (m, 4 H), 8.06 (t, J = 7.6 Hz, 1 H), 7.93–7.89 (m, 2 H), 7.65 (d, J = 8.3 Hz, 2 H), 7.53–7.48 (m, 3 H).

¹³C NMR (~101 MHz, CDCl₃): δ = 161.9, 149.3, 148.0, 147.5, 137.6, 134.8, 131.9, 131.8, 131.2, 130.6, 129.9, 129.8, 129.6, 127.8, 126.9, 126.8, 126.6, 126.5, 126.4, 126.2, 125.3, 124.8, 124.5, 122.0, 118.6, 110.3.

HRMS (ESI): m/z [M + H]⁺ calcd for C₂₉H₁₈N₃O: 424.1450; found: 424.1467.

N-(10-(4-Chlorophenyl)pyren-1-yl)picolinamide (5m)

By following the general procedure, 5m was obtained after purification by column chromatography on silica gel (EtOAc/hexane = 20:80) as a brown solid (37 mg, 58%, 0.15 mmol scale).

R_f = 0.5 (EtOAc/hexane = 20:80); mp 200–202 °C.

IR (DCM): 3440, 3332, 1678, 1517, 1486 cm^–1.

¹H NMR (400 MHz, DMSO-d ₆): δ = 10.04 (s, 1 H), 8.44–8.40 (m, 3 H), 8.33 (d, J = 7.5 Hz, 1 H), 8.28 (d, J = 7.5 Hz, 1 H), 8.25–8.19 (m, 2 H), 8.09 (t, J = 7.6 Hz, 1 H), 7.99–7.97 (m, 3 H), 7.62–7.58 (m, 1 H), 7.44 (d, J = 8.2 Hz, 2 H), 7.21 (d, J = 8.2 Hz, 2 H).

¹³C NMR (~101 MHz, CDCl₃): δ = 162.0, 149.5, 147.7, 141.5, 137.2, 135.4, 133.2, 131.7, 131.3, 131.2, 130.3, 130.2, 129.4, 128.5, 127.8, 126.6, 126.4, 126.4, 126.3, 126.3, 125.6, 124.9, 124.4, 123.9, 121.9, 121.7.

HRMS (ESI): m/z [M + H]⁺ calcd for C₂₈H₁₈ClN₂O: 433.1108; found: 433.1100.

N-(10-(4-Bromophenyl)pyren-1-yl)picolinamide (5n)

By following the general procedure, compound 5n was obtained after purification by column chromatography on silica gel (EtOAc/hexane = 20:80) as a brown solid (50 mg, 53%).

R_f = 0.5 (EtOAc/hexane = 20:80); mp 165–167 °C.

IR (DCM): 3325, 2959, 1678, 1521, 1467 cm^–1.

¹H NMR (400 MHz, DMSO-d ₆): δ = 10.08 (s, 1 H), 8.46–8.29 (m, 6 H), 8.26–8.21 (m, 2 H), 8.11 (t, J = 7.6 Hz, 1 H), 8.00–7.96 (m, 3 H), 7.63–7.60 (m, 1 H), 7.39 (d, J = 8.4 Hz, 2 H), 7.35 (d, J = 8.4 Hz, 2 H).

¹³C NMR (~126 MHz, CDCl₃): δ = 161.0, 148.4, 146.8, 140.9, 136.2, 134.3, 130.6, 130.4, 130.3, 130.1, 129.6, 129.1, 128.4, 126.7, 125.6, 125.4, 125.3, 124.6, 123.9, 123.4, 123.0, 120.9, 120.7, 120.3.

HRMS (ESI): m/z [M + H]⁺ calcd for C₂₈H₁₈BrN₂O: 477.0603; found: 477.0607.

N-(10-(3,5-Dimethylphenyl)pyren-1-yl)picolinamide (5o)

By following the general procedure, compound 5o was obtained after purification by column chromatography on silica gel (EtOAc/hexane = 20:80) as a brown solid (38 mg, 45%).

R_f = 0.5 (EtOAc/hexane = 20:80); mp 165–167 °C.

IR (DCM): 3313, 1678, 1511, 1434, 840 cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 9.75 (s, 1 H), 8.65 (d, J = 8.4 Hz, 1 H), 8.31–8.28 (m, 2 H), 8.19 (d, J = 7.4 Hz, 2 H), 8.13–8.06 (m, 3 H), 8.01 (t, J = 7.6 Hz, 1 H), 7.93 (s, 1 H), 7.83 (td, ¹ J = 7.7 Hz, 1 H, ² J = 1.6 Hz), 7.41–7.38 (m, 1 H), 7.16 (s, 2 H), 6.59 (s, 1 H), 2.20 (s, 6 H).

¹³C NMR (~101 MHz, CDCl₃): δ = 162.1, 149.8, 147.2, 142.9, 137.8, 136.9, 131.4, 131.3, 131.1, 130.4, 129.5, 128.4, 127.8, 126.8, 126.6, 126.5, 126.3, 126.0, 125.9, 125.3, 124.7, 124.3, 122.4, 121.8, 21.2.

HRMS (ESI): m/z [M + H]⁺ calcd for C₃₀H₂₃N₂O: 427.1810; found: 427.1826.

N-(10-(3,4-Dimethylphenyl)pyren-1-yl)picolinamide (5p)

By following the general procedure, compound 5p was obtained after purification by column chromatography on silica gel (EtOAc/hexane = 20:80) as a brown solid (55 mg, 65%).

R_f = 0.5 (EtOAc/hexane = 20:80); mp 148–150 °C.

IR (DCM): 3428, 1686, 1590, 1517, 1128 cm^–1.

¹H NMR (400 MHz, DMSO-d ₆): δ = 9.88 (s, 1 H), 8.44–8.38 (m, 2 H), 8.33–8.18 (m, 5 H), 8.08 (t, J = 7.6 Hz, 1 H), 7.98–7.95 (m, 3 H), 7.59–7.55 (m, 1 H), 7.19 (s, 1 H), 7.15–7.12 (m, 1 H), 6.92 (d, J = 7.6 Hz, 1 H), 2.04 (s, 3 H), 1.90 (s, 3 H).

¹³C NMR (~101 MHz, CDCl₃): δ = 162.0, 150.0, 147.3, 140.5, 136.9, 136.8, 136.4, 135.3, 131.4, 131.3, 130.5, 130.3, 129.7, 129.4, 127.8, 126.6, 126.5, 126.3, 126.3, 126.3, 126.0, 125.8, 125.2, 124.7, 124.3, 124.1, 122.2, 121.8, 19.5, 19.3.

HRMS (ESI): m/z [M + H]⁺ calcd for C₃₀H₂₃N₂O: 427.1810; found: 427.1801.

N-(10-(2,3-Dihydrobenzo[b][1,4]dioxin-6-yl)pyren-1-yl)picolinamide (5q)

By following the general procedure, compound 5q was obtained after purification by column chromatography on silica gel (EtOAc/hexane = 20:80) as a brown solid (56 mg, 62%).

R_f = 0.3 (EtOAc/hexane = 20:80); mp 192–194 °C.

IR (DCM): 3448, 2925, 1686, 1517, 1252 cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 10.06 (s, 1 H), 8.79 (d, J = 8.3 Hz, 1 H), 8.43–8.42 (m, 1 H), 8.30–8.23 (m, 2 H), 8.18 (d, J = 7.1 Hz, 1 H), 8.11–7.98 (m, 4 H), 7.92 (s, 1 H), 7.86 (t, ¹ J = 7.7 Hz, 1 H, ² J = 1.6 Hz), 7.44–7.41 (m, 1 H), 7.10–7.06 (m, 2 H), 6.84 (d, J = 8.0 Hz, 1 H), 4.20–4.13 (m, 2 H), 3.98–3.91 (m, 2 H).

¹³C NMR (~101 MHz, CDCl₃): δ = 161.9, 150.1, 147.5, 143.4, 143.0, 137.2, 136.2, 136.0, 131.5, 131.5, 131.3, 130.4, 129.2, 127.7, 126.5, 126.3, 126.1, 125.9, 125.3, 124.7, 124.3, 123.4, 122.3, 122.1, 121.7, 118.0, 117.3, 64.3, 64.2.

HRMS (ESI): m/z [M + H]⁺ calcd for C₃₀H₂₁N₂O₃: 457.1552; found: 457.1541.

N-(10-(6-Chloropyridin-3-yl)pyren-1-yl)picolinamide (5r)

By following the general procedure, compound 5r was obtained after purification by column chromatography on silica gel (EtOAc/hexane = 25:75) as a brown solid (36 mg, 42%).

R_f = 0.3 (EtOAc/hexane = 20:80); mp 194–196 °C.

IR (DCM): 3323, 1678, 1513, 1274, 842 cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 9.72 (s, 1 H), 8.72 (s, 1 H), 8.65 (d, J = 8.3 Hz, 1 H), 8.43 (d, J = 4.4 Hz, 1 H), 8.23–8.17 (m, 3 H), 8.09–7.97 (m, 4 H), 7.88 (t, J = 7.6 Hz, 1 H), 7.81 (s, 1 H), 7.56 (d, J = 8.1 Hz, 1 H), 7.47 (t, J = 6.2 Hz, 1 H), 6.99 (d, J = 8.2 Hz, 1 H).

¹³C NMR (~101 MHz, CDCl₃): δ = 161.6, 150.1, 149.1, 148.4, 148.0, 139.4, 137.6, 137.5, 132.3, 131.3, 131.2, 130.7, 129.8, 129.4, 127.7, 126.7, 126.6, 126.5, 126.3, 126.1, 125.2, 124.4, 123.7, 123.4, 122.0, 121.3.

HRMS (ESI): m/z [M + H]⁺ calcd for C₂₇H₁₇ClN₃O: 434.1060; found: 434.1045.

N-(10-(5-Bromopyridin-2-yl)pyren-1-yl)picolinamide (5s)

By following the general procedure, compound 5s was obtained after purification by column chromatography on silica gel (EtOAc/hexane = 25:75) as a brown solid (48 mg, 51%).

R_f = 0.3 (EtOAc/hexane = 20:80); mp 175–177 °C.

IR (DCM): 3344, 2936, 1682, 1521, 1236 cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 9.80 (s, 1 H), 8.80–8.79 (m, 1 H), 8.50–8.47 (m, 2 H), 8.33 (d, J = 8.3 Hz, 1 H), 8.26 (d, J = 7.6 Hz, 1 H), 8.19–8.12 (m, 4 H), 8.10–8.03 (m, 2 H), 7.87 (td, ¹ J = 7.7 Hz, ² J = 1.6 Hz, 1 H), 7.60 (dd, ¹ J = 8.4 Hz, ² J = 2.4 Hz, 1 H), 7.49–7.45 (m, 1 H), 7.42 (d, J = 8.3 Hz, 1 H).

¹³C NMR (~101 MHz, CDCl₃): δ = 162.5, 160.2, 150.6, 149.3, 147.9, 138.7, 137.4, 134.7, 132.4, 131.2, 130.6, 130.0, 129.9, 127.8, 126.9, 126.5, 126.4, 126.4, 126.2, 125.6, 125.5, 125.4, 124.7, 122.8, 122.1, 118.9.

HRMS (ESI): m/z [M + H]⁺ calcd for C₂₇H₁₇BrN₃O: 478.0555; found: 478.0538.

N-(10-(Thiophen-2-yl)pyren-1-yl)picolinamide (5t)

By following the general procedure, compound 5t was obtained after purification by column chromatography on silica gel (EtOAc/hexane = 20:80) as a brown solid (57 mg, 71%).

R_f = 0.5 (EtOAc/hexane = 20:80); mp 148–150 °C.

IR (DCM): 3428, 2932, 1675, 1513, 1321 cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 10.31 (s, 1 H), 8.84 (d, J = 8.4 Hz, 1 H), 8.41 (d, J = 4.3 Hz, 1 H), 8.32 (d, J = 8.4 Hz, 1 H), 8.23 (d, J = 7.6 Hz, 2 H), 8.15–8.01 (m, 5 H), 7.88–7.84 (m, 1 H), 7.44–7.41 (m, 1 H), 7.25 (dd, ¹ J = 7.6 Hz, ² J = 0.9 Hz, 1 H), 7.17 (dd, ¹ J = 5.2 Hz, ² J = 0.9 Hz, 1 H), 6.91 (dd, ¹ J = 5.2 Hz, ² J = 3.6 Hz, 1 H).

¹³C NMR (~101 MHz, CDCl₃): δ = 162.2, 150.0, 147.6, 143.8, 137.1, 133.5, 131.7, 131.3, 129.9, 129.1, 128.6, 127.8, 127.6, 127.2, 126.4, 126.3, 126.3, 126.0, 125.8, 125.7, 124.9, 124.6, 123.4, 122.0, 121.9.

HRMS (ESI): m/z [M + H]⁺ calcd for C₂₆H₁₇N₂OS: 405.1062; found: 405.1073.

2-(4-Methoxyphenyl)-N-(2-(methylthio)phenyl)pyrene-1-carboxamide (6a)

By following the general procedure, compound 6a was obtained after purification by column chromatography on silica gel (EtOAc/hexane = 20:80) as a brown solid (53 mg, 56%).

R_f = 0.4 (EtOAc/hexane = 20:80); mp 151–153 °C.

IR (DCM): 3348, 2925, 1667, 1582, 1509 cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 8.58 (d, J = 8.1 Hz, 1 H), 8.49 (s, 1 H), 8.44 (d, J = 9.2 Hz, 1 H), 8.25–8.04 (m, 7 H), 7.76 (d, J = 8.6 Hz, 2 H), 7.46–7.38 (m, 2 H), 7.14–7.10 (m, 1 H), 7.02 (d, J = 8.6 Hz, 2 H), 3.83 (s, 3 H), 2.05 (s, 3 H).

¹³C NMR (~101 MHz, CDCl₃): δ = 168.5, 159.4, 138.4, 136.3, 133.1, 133.0, 132.0, 131.1, 130.6, 129.1, 128.9, 128.7, 127.1, 126.3, 126.3, 126.1, 125.9, 125.8, 124.8, 124.5, 124.3, 123.5, 120.8, 114.3, 55.4, 18.9.

HRMS (ESI): m/z [M + H]⁺ calcd for C₃₁H₂₄NO₂S: 474.1528; found: 474.1538.

N-(2-(Methylthio)phenyl)-2-(thiophen-2-yl)pyrene-1-carbox­amide (6b)

By following the general procedure, compound 6b was obtained after purification by column chromatography on silica gel (EtOAc/hexane = 20:80) as a brown solid (51 mg, 57%).

R_f = 0.5 (EtOAc/hexane = 20:80); mp 167–169 °C.

IR (DCM): 3336, 2921, 1678, 1509, 1428 cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 8.69–8.64 (m, 2 H), 8.39–8.36 (m, 2 H), 8.28–8.25 (m, 2 H), 8.21–8.19 (m, 2 H), 8.14–8.06 (m, 2 H), 7.55 (d, J = 3.1 Hz, 1 H), 7.50–7.41 (m, 3 H), 7.17–7.12 (m, 2 H), 2.08 (s, 3 H).

¹³C NMR (~101 MHz, DMSO-d ₆): δ = 168.2, 141.9, 135.6, 135.1, 132.3, 131.4, 131.2, 130.7, 129.7, 129.2, 129.1, 128.4, 128.0, 128.0, 127.6, 127.6, 127.3, 127.0, 127.0, 126.5, 126.3, 126.3, 125.6, 125.3, 123.9, 123.3.

HRMS (ESI): m/z [M + H]⁺ calcd for C₂₈H₂₀NOS₂: 450.0986; found: 450.0999.

N-(tert-Butyl)-9-(p-tolyl)pyrene-1-carboxamide (8a)

By following the general procedure, compound 8a was obtained after purification by column chromatography on silica gel (EtOAc/hexane = 20:80) as a pale-yellow solid (41 mg, 53%).

R_f = 0.5 (EtOAc/hexane = 20:80); mp 161–163 °C.

IR (DCM): 3259, 2959, 1675, 1632, 1540 cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 8.50 (s, 1 H), 8.30 (d, J = 7.9 Hz, 1 H), 8.25 (d, J = 7.6 Hz, 1 H), 8.16–8.13 (m, 2 H), 8.10–8.06 (m, 2 H), 7.99 (t, J = 7.8 Hz, 1 H), 7.59 (d, J = 7.9 Hz, 2 H), 7.40 (d, J = 7.8 Hz, 2 H), 6.00–5.99 (m, 1 H), 2.54 (s, 3 H), 1.59 (s, 9 H).

¹³C NMR (~101 MHz, CDCl₃): δ = 169.6, 140.6, 137.9, 137.3, 132.6, 132.1, 131.4, 130.2, 130.1, 129.2, 128.6, 128.1, 127.0, 126.1, 125.9, 124.9, 124.7, 124.7, 124.6, 124.3, 124.1, 52.3, 29.1, 21.4.

HRMS (ESI): m/z [M + H]⁺ calcd for C₂₈H₂₆NO: 392.2014; found: 392.1998.

N-(tert-Butyl)-9-phenylpyrene-1-carboxamide (8b)

By following the general procedure, compound 8b was obtained after purification by column chromatography on silica gel (EtOAc/hexane = 20:80) as a pale-yellow solid (41 mg, 55%).

R_f = 0.5 (EtOAc/hexane = 20:80); mp 158–160 °C.

IR (DCM): 3340, 2925, 1707, 1673, 1518 cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 8.51 (s, 1 H), 8.27–8.22 (m, 2 H), 8.14–7.97 (m, 5 H), 7.69 (d, J = 7.1 Hz, 2 H), 7.60 (t, J = 7.6 Hz, 2 H), 7.54 (d, J = 7.2 Hz, 1 H), 6.08 (s, 1 H), 1.59 (s, 9 H).

¹³C NMR (~101 MHz, CDCl₃): δ = 169.5, 140.8, 140.6, 132.6, 132.1, 131.4, 130.2, 130.0, 128.6, 128.5, 128.0, 127.6, 127.0, 126.1, 125.9, 124.9, 124.8, 124.6, 124.6, 124.2, 124.1, 52.3, 29.1.

HRMS (ESI): m/z [M + H]⁺ calcd for C₂₇H₂₄NO: 378.1858; found: 378.1845.

2-Butyl-N-(quinolin-8-yl)pyrene-1-carboxamide (10a)

By following the general procedure, compound 10a was obtained after­ purification by column chromatography on silica gel (EtOAc/ hexane = 20:80) as a pale-yellow solid (41 mg, 70%, 0.14 mmol scale).

R_f = 0.5 (EtOAc/hexane = 20:80); mp 167–169 °C.

IR (DCM): 3342, 2954, 1667, 1515, 1479 cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 10.29 (s, 1 H), 9.23 (dd, ¹ J = 7.6 Hz, ² J = 1.2 Hz, 1 H), 8.64 (dd, ¹ J = 4.2 Hz, ² J = 1.6 Hz, 1 H), 8.27 (d, J = 9.2 Hz, 1 H), 8.24–8.19 (m, 3 H), 8.15–8.07 (m, 4 H), 8.02 (t, J = 7.6 Hz, 1 H), 7.73 (t, J = 8.1 Hz, 1 H), 7.65 (dd, ¹ J = 8.3 Hz, ² J = 1.2 Hz, 1 H), 7.43 (dd, ¹ J = 8.3 Hz, ² J = 4.2 Hz, 1 H), 3.21 (t, J = 8.0 Hz, 2 H), 1.98–1.90 (m, 2 H), 1.48–1.41 (m, 2 H), 0.9 (t, J = 7.3 Hz, 3 H).

¹³C NMR (~126 MHz, CDCl₃): δ = 168.8, 148.3, 138.5, 137.3, 136.3, 134.6, 132.4, 131.8, 130.9, 130.5, 128.6, 128.3, 128.1, 128.0, 127.5, 127.0, 125.9, 125.7, 125.6, 125.4, 124.4, 124.3, 123.0, 122.1, 121.7, 34.3, 33.9, 22.8, 14.0.

HRMS (ESI): m/z [M + H]⁺ calcd for C₃₀H₂₅N₂O: 429.1967; found: 429.1948.

2-Pentyl-N-(quinolin-8-yl)pyrene-1-carboxamide (10b)

By following the general procedure, compound 10b was obtained after­ purification by column chromatography on silica gel (EtOAc/ hexane­ = 20:80) as a pale-yellow solid (31 mg, 71%, 0.1 mmol scale).

R_f = 0.6 (EtOAc/hexane = 20:80); mp 148–150 °C.

IR (DCM): 3343, 2926, 1669, 1515, 1480 cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 10.28 (s, 1 H), 9.23 (dd, ¹ J = 7.6 Hz, ² J = 1.1 Hz, 1 H), 8.64 (dd, ¹ J = 4.2 Hz, ² J = 1.6 Hz, 1 H), 8.28–8.19 (m, 4 H), 8.15–8.01 (m, 4 H), 8.03 (t, J = 7.6 Hz, 1 H), 7.73 (t, J = 7.8 Hz, 1 H), 7.64 (dd, ¹ J = 8.3 Hz, ² J = 1.1 Hz, 1 H), 7.2 (dd, ¹ J = 8.3 Hz, ² J = 4.2 Hz, 1 H), 3.20 (t, J = 7.8 Hz, 2 H), 1.97–1.92 (m, 2 H), 1.42–1.28 (m, 4 H), 0.82 (t, J = 7.2 Hz, 3 H).

¹³C NMR (~126 MHz, CDCl₃): δ = 167.7, 147.3, 137.5, 136.3, 135.3, 133.6, 131.4, 130.8, 129.9, 129.5, 127.5, 127.3, 127.0, 127.0, 126.5, 126.0, 124.9, 124.7, 124.5, 124.4, 123.4, 123.3, 122.0, 121.1, 120.7, 115.8, 33.1, 30.8, 28.7, 21.5, 12.9.

HRMS (ESI): m/z [M + H]⁺ calcd for C₃₁H₂₇N₂O: 443.2123; found: 443.2107.

2-Heptyl-N-(quinolin-8-yl)pyrene-1-carboxamide (10c)

By following the general procedure, compound 10c was obtained after­ purification by column chromatography on silica gel (EtOAc/ hexane­ = 10:80) as a pale-yellow solid (52 mg, 74%, 0.15 mmol scale).

R_f = 0.7 (EtOAc/hexane = 20:80); mp 108–110 °C.

IR (DCM): 3346, 2925, 1707, 1673, 1518 cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 10.32 (s, 1 H), 9.26 (dd, ¹ J = 7.6 Hz, ² J = 1.2 Hz, 1 H), 8.63 (dd, ¹ J = 4.2 Hz, ² J = 1.6 Hz, 1 H), 8.29 (d, J = 9.2 Hz, 1 H), 8.22–8.16 (m, 3 H), 8.14–8.00 (m, 5 H), 7.73 (t, J = 8.1 Hz, 1 H), 7.63 (dd, ¹ J = 8.3 Hz, ² J = 1.2 Hz, 1 H), 7.40 (dd, ¹ J = 8.3 Hz, ² J = 4.2 Hz, 1 H), 3.22 (t, J = 8.0 Hz, 2 H), 1.98–1.92 (m, 2 H), 1.46–1.38 (m, 2 H), 1.32–1.25 (m, 2 H), 1.22–1.16 (m, 4 H), 0.8 (t, 3 H, J = 6.8 Hz).

¹³C NMR (~101 MHz, CDCl₃): δ = 168.8, 148.3, 138.5, 137.4, 136.3, 134.6, 132.5, 131.8, 131.0, 130.5, 128.6, 128.3, 128.1, 127.5, 127.0, 125.9, 125.8, 125.6, 125.5, 124.5, 124.3, 123.0, 122.2, 121.7, 116.9, 34.2, 32.2, 31.7, 29.7, 29.2, 22.6, 14.1.

HRMS (ESI): m/z [M + H]⁺ calcd for C₃₃H₃₁N₂O: 471.2436; found: 471.2423.

2-Octyl-N-(quinolin-8-yl)pyrene-1-carboxamide (10d)

By following the general procedure, compound 10d was obtained after­ purification by column chromatography on silica gel (EtOAc/ hexane­ = 10:90) as a pale-yellow solid (35 mg, 73%, 0.1 mmol scale).

R_f = 0.7 (EtOAc/hexane = 20:80); mp 152–154 °C.

IR (DCM): 3359, 2932, 1655, 1528, 1475 cm^–1.

¹H NMR (400 MHz, DMSO-d ₆): δ = 10.44 (s, 1 H), 8.92 (dd, ¹ J = 7.5 Hz, ² J = 1.1 Hz, 1 H), 8.76 (dd, ¹ J = 4.2 Hz, ² J = 1.6 Hz, 1 H), 8.48 (dd, ¹ J = 8.3 Hz, ² J = 1.5 Hz, 1 H), 8.37–8.31 (m, 3 H), 8.28–8.16 (m, 4 H), 8.11 (t, J = 7.6 Hz, 1 H), 7.84 (dd, ¹ J = 8.3 Hz, ² J = 1.1 Hz, 1 H), 7.79–7.75 (m, 1 H), 7.62 (dd, ¹ J = 8.2 Hz, ² J = 4.2 Hz, 1 H), 3.12–3.08 (m, 2 H), 1.86–1.82 (m, 2 H), 1.34–0.97 (m, 10 H), 0.71 (t, J = 7.2 Hz, 3 H).

¹³C NMR (~101 MHz, CDCl₃): δ = 168.8, 148.3, 138.5, 137.4, 136.3, 134.6, 132.5, 131.8, 131.0, 130.5, 128.6, 128.3, 128.1, 127.5, 127.0, 125.9, 125.8, 125.6, 125.5, 124.5, 124.3, 123.0, 122.1, 121.7, 116.9, 34.2, 32.2, 31.8, 29.7, 29.4, 29.2, 22.6, 14.1.

HRMS (ESI): m/z [M + H]⁺ calcd for C₃₄H₃₃N₂O: 485.2593; found: 485.2571.

N-(10-Butylpyren-1-yl)picolinamide (11a)

By following the general procedure, compound 11a was obtained after­ purification by column chromatography on silica gel (EtOAc/ hexane = 15:85) as a brown solid (51 mg, 68%).

R_f = 0.6 (EtOAc/hexane = 20:80); mp 144–146 °C.

IR (DCM): 3396, 2951, 1678, 1556, 1514 cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 10.8 (s, 1 H), 8.72 (d, J = 4.3 Hz, 1 H), 8.53 (d, J = 8.3 Hz, 1 H), 8.45 (d, J = 7.8 Hz, 1 H), 8.23 (d, J = 8.3 Hz, 1 H), 8.16–8.13 (m, 1 H), 8.08–8.03 (m, 3 H), 8.01–7.96 (m, 2 H), 7.91 (s, 1 H), 7.56–7.53 (m, 1 H), 3.48 (t, J = 7.9 Hz, 2 H), 1.78–1.72 (m, 2 H), 1.32–1.26 (m, 2 H), 0.84 (t, J = 7.4 Hz, 3 H).

¹³C NMR (~101 MHz, CDCl₃): δ = 162.5, 150.2, 148.1, 137.7, 136.5, 131.2, 130.9, 130.8, 130.2, 129.8, 127.7, 127.0, 126.8, 126.6, 126.1, 125.7, 125.3, 124.8, 124.7, 124.1, 124.1, 122.7, 38.0, 33.9, 22.7, 13.9.

HRMS (ESI): m/z [M + H]⁺ calcd for C₂₆H₂₃N₂O: 379.1810; found: 379.1794.

N-(10-Pentylpyren-1-yl)picolinamide (11b)

By following the general procedure, compound 11b was obtained after­ purification by column chromatography on silica gel (EtOAc/ hexane­ = 20:80) as a brown solid (69 mg, 88%).

R_f = 0.5 (EtOAc/hexane = 20:80); mp 128–130 °C.

IR (DCM): 3352, 2936, 1686, 1513, 1325 cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 10.79 (s, 1 H), 8.74–8.73 (m, 1 H), 8.53 (d, J = 8.3 Hz, 1 H), 8.46 (d, J = 7.8 Hz, 1 H), 8.25 (d, J = 8.3 Hz, 1 H), 8.17–8.15 (m, 1 H), 8.11–8.05 (m, 3 H), 8.02–7.97 (m, 2 H), 7.94 (s, 1 H), 7.59–7.56 (m, 1 H), 3.50 (t, J = 8.0 Hz, 2 H), 1.80–1.76 (m, 2 H), 1.28–1.22 (m, 4 H), 0.78 (t, J = 6.9 Hz, 3 H).

¹³C NMR (~101 MHz, CDCl₃): δ = 162.5, 150.2, 148.1, 137.8, 136.6, 131.2, 130.9, 130.8, 130.2, 129.9, 127.8, 127.0, 126.8, 126.6, 126.1, 125.7, 125.4, 124.9, 124.8, 124.2, 124.1, 122.8, 38.4, 31.8, 31.6, 22.6, 14.1.

HRMS (ESI): m/z [M + H]⁺ calcd for C₂₇H₂₅N₂O: 393.1967; found: 393.1957.

N-(10-Heptylpyren-1-yl)picolinamide (11c)

By following the general procedure, compound 11c was obtained after­ purification by column chromatography on silica gel (EtOAc/ hexane = 20:80) as a brown solid (48 mg, 58%).

R_f = 0.6 (EtOAc/hexane = 20:80); mp 132–134 °C.

IR (DCM): 3375, 2928, 1690, 1517, 1321 cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 10.77 (s, 1 H), 8.73 (d, J = 4.6 Hz, 1 H), 8.52 (d, J = 8.2 Hz, 1 H), 8.46 (d, J = 7.8 Hz, 1 H), 8.24 (d, J = 8.2 Hz, 1 H), 8.15 (d, J = 7.5 Hz, 1 H), 8.09–8.06 (m, 3 H), 8.01–7.97 (m, 2 H), 7.92 (s, 1 H), 7.58–7.55 (m, 1 H), 3.48 (t, J = 7.8 Hz, 2 H), 1.78–1.74 (m, 2 H), 1.22–1.13 (m, 8 H), 0.84 (t, J = 7.1 Hz, 3 H).

¹³C NMR (~101 MHz, CDCl₃): δ = 162.5, 150.2, 148.1, 137.8, 136.6, 131.2, 130.9, 130.8, 130.2, 129.9, 127.8, 127.0, 126.8, 126.6, 126.1, 125.7, 125.4, 124.8, 124.8, 124.1, 124.1, 122.8, 38.4, 31.9, 31.9, 29.7, 29.2, 22.6, 14.1.

HRMS (ESI): m/z [M + H]⁺ calcd for C₂₉H₂₉N₂O: 421.2280; found: 421.2265.

10-(4-Methoxyphenyl)pyren-1-amine (12a)

By following the general procedure, compound 12a was obtained after­ purification by column chromatography on silica gel (EtOAc/ hexane = 5:95) as a brown solid (27 mg, 56%, 0.15 mmol scale).

R_f = 0.8 (EtOAc/hexane = 20:80); mp 134–136 °C.

IR (DCM): 3484, 3386, 1601, 1510, 1450 cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 8.07–7.91 (m, 5 H), 7.84 (d, J = 8.7 Hz, 1 H), 7.72 (s, 1 H), 7.54 (d, J = 7.9 Hz, 2 H), 7.23 (d, J = 8.2 Hz, 1 H), 7.07 (d, J = 7.9 Hz, 2 H), 3.94 (s, 3 H). The NH₂ signal could not be clearly located in the proton NMR spectrum.

¹³C NMR (~101 MHz, CDCl₃): δ = 159.2, 142.8, 137.1, 135.6, 132.4, 131.2, 130.3, 129.1, 128.0, 127.4, 127.1, 126.2, 125.2, 124.2, 123.8, 123.3, 122.8, 115.9, 114.5, 113.9, 55.4.

HRMS (ESI): m/z [M + H]⁺ calcd for C₂₃H₁₈NO: 324.1388; found: 324.1373.

10-(Thiophen-2-yl)pyren-1-amine (12b)

By following the general procedure, compound 12b was obtained after­ purification by column chromatography on silica gel (EtOAc/ hexane = 5:95) as a brown solid (25 mg, 70%, 0.12 mmol scale).

R_f = 0.8 (EtOAc/hexane = 20:80); mp 169–171 °C.

IR (DCM): 3471, 3398, 2928, 1617, 1452 cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 8.07 (d, J = 7.3 Hz, 1 H), 8.02 (d, J = 8.2 Hz, 1 H), 7.97–7.91 (m, 4 H), 7.83 (d, J = 8.8 Hz, 1 H), 7.52 (d, J = 5.2 Hz, 1 H), 7.28–7.26 (m, 2 H), 7.22–7.20 (m, 1 H), 4.25 (br s, 2 H).

¹³C NMR (~101 MHz, CDCl₃): δ = 144.3, 143.0, 132.4, 131.2, 130.7, 129.1, 128.0, 127.6, 127.3, 127.1, 126.3, 126.2, 125.6, 124.4, 124.0, 123.2, 123.0, 116.2, 114.5.

HRMS (ESI): m/z [M + H]⁺ calcd for C₂₀H₁₄NS: 300.0847; found: 300.0844.

10-(p-Tolyl)pyren-1-amine (12c)

By following the general procedure, compound 12c was obtained after­ purification by column chromatography on silica gel (EtOAc/ hexane = 5:95) as a red solid (112 mg, 73%, 0.5 mmol).

R_f = 0.9 (EtOAc/hexane = 20:80); mp 150–152 °C.

IR (DCM): 3494, 3398, 1617, 1513, 1452 cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 8.07–7.93 (m, 5 H), 7.87–7.84 (m, 1 H), 7.73–7.72 (m, 1 H), 7.53–7.51 (m, 2 H), 7.37–7.35 (m, 2 H), 7.23 (d, J = 8.0 Hz, 1 H), 4.13 (br s, 2 H), 2.53 (s, 3 H).

¹³C NMR (~101 MHz, CDCl₃): δ = 143.0, 140.5, 137.5, 132.4, 131.3, 129.2, 129.1, 128.9, 128.0, 127.4, 127.1, 126.2, 125.3, 124.1, 123.8, 123.2, 122.8, 115.9, 114.3, 21.4.

HRMS (ESI): m/z [M + H]⁺ calcd for C₂₃H₁₈N: 308.1439; found: 308.1428.

10-(4-Butylphenyl)pyren-1-amine (12d)

Compound 12d was obtained via a one-pot sequential C–H arylation of 2b under standard reaction conditions and neat conditions, followed by NaOH-mediated hydrolysis procedure. After the standard work-up procedure and purification by column chromatography on silica gel (EtOAc/hexane = 5:95) as a red solid (32 mg, 46%, 0.2 mmol scale from 2b).

R_f = 0.9 (EtOAc/hexane = 20:80); mp 142–144 °C.

IR (DCM): 3490, 3394, 1613, 1513, 1421 cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 8.06–8.01 (m, 2 H), 8.00–7.90 (m, 3 H), 7.83 (d, J = 8.8 Hz, 1 H), 7.72 (s, 1 H), 7.53 (d, J = 8.0 Hz, 2 H), 7.36 (d, J = 8.0 Hz, 2 H), 7.23 (d, J = 8.2 Hz, 1 H), 4.13 (s, 2 H), 2.77 (t, J = 7.8 Hz, 2 H), 1.77–1.70 (m, 2 H), 1.50–1.44 (m, 2 H), 1.02 (t, J = 7.4 Hz, 3 H).

¹³C NMR (~101 MHz, CDCl₃): δ = 143.0, 142.5, 140.7, 137.5, 132.4, 131.2, 129.0, 128.9, 128.5, 128.0, 127.4, 127.1, 126.2, 125.3, 124.1, 123.7, 123.2, 122.8, 115.8, 114.3, 35.5, 33.7, 22.5, 14.1.

HRMS (ESI): m/z [M + H]⁺ calcd for C₂₆H₂₄N: 350.1909; found: 350.1897.

Conflict of Interest

The authors declare no conflict of interest.

Acknowledgment

We thank IISER Mohali for use of the analytical (NMR, HRMS and X-ray) facilities.

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Publication History

Received: 09 March 2021

Accepted after revision: 31 March 2021

Accepted Manuscript online:
31 March 2021

Article published online:
26 April 2021