Indium-Catalyzed Friedel–Crafts Alkylation of Monosubstituted Benzenes by 1-Bromoadamantane

Paul Mosset; René Grée

doi:10.1055/s-0032-1316909

Synlett, Inhaltsverzeichnis

Synlett 2013; 24(9): 1142-1146
DOI: 10.1055/s-0032-1316909

letter

Indium-Catalyzed Friedel–Crafts Alkylation of Monosubstituted Benzenes by 1-Bromoadamantane

Paul Mosset*

Université de Rennes 1, Institut des Sciences Chimiques de Rennes, CNRS UMR 6226, Avenue du Général Leclerc, 35042 Rennes Cedex, France Fax: +33(2)23236978 eMail: paul.mosset.1@univ-rennes1.fr

,

René Grée

Université de Rennes 1, Institut des Sciences Chimiques de Rennes, CNRS UMR 6226, Avenue du Général Leclerc, 35042 Rennes Cedex, France Fax: +33(2)23236978 eMail: paul.mosset.1@univ-rennes1.fr

› Institutsangaben

Abstract

Alle Artikel dieser Rubrik

Abstract

Indium salts such as InCl₃ and InBr₃ (ca. 1–5 mol%) efficiently catalyzed the Friedel–Crafts reaction of 1-bromoadamantane with benzene and monosubstituted benzenes to give 1-adamantyl benzenes. Indium bromide enabled faster reactions than indium chloride but the latter was more suitable in the case of halobenzenes.

Key words

adamantanes - alkylation - catalysis - indium - Lewis acids

Volltext

Referenzen

References and Notes

1a Friedel C, Crafts J.-M. Compt. Rend. 1877; 84: 1392
1b Friedel C, Crafts J.-M. Compt. Rend. 1877; 84: 1450

2a Friedel–Crafts and Related Reactions . Vols. I–IV. Olah GA. Wiley-Interscience; New York: 1964
2b Olah GA In Friedel–Crafts Chemistry . Wiley-Interscience; New York: 1973
2c Roberts RM, Khalaf AA In Friedel–Crafts Alkylation Chemistry: A Century of Discovery. Dekker; New York: 1984
2d Olah GA, Krishnamurthi R, Prakash GK. S In Friedel–Crafts Alkylations in Comprehensive Organic Synthesis . Trost BM, Fleming I. Pergamon Press; Oxford: 1991
2e Bandini M, Melloni A, Umani-Ronchi A. Angew. Chem. Int. Ed. 2004; 43: 550
2f Rueping M, Nachtsheim BJ. Beilstein J. Org. Chem. 2010; 6 doi: 10.3762/bjoc.6.6
2g Sartori G, Maggi R In Advances in Friedel–Crafts Acylation Reactions, Catalytic and Green Processes . CRC Press, Taylor & Francis Group; Boca Raton/London/New York: 2010

For reviews for indium Lewis acids, see:

3a Frost CG, Chauhan KK. J. Chem. Soc., Perkin Trans. 1 2000; 3015
3b Fringuelli F, Piermatti O, Pizzo F, Vaccaro L. Curr. Org. Chem. 2003; 7: 1661
3c Frost CG, Hartley JP. Mini-Rev. Org. Chem. 2004; 1: 1
3d Yadav JS, Antony A, George J, Subba Reddy BV. Eur. J. Org. Chem. 2010; 591
3e Shankar Singh M, Raghuvanshi K. Tetrahedron 2012; 68: 8683
3f For organoindium species, see: Xu B, Hammond GB. Chem. Eur. J. 2008; 14: 10029

4 Hayashi R, Cook GR. Org. Lett. 2007; 9: 1311 ; and references cited within

5a Kaneko M, Hayashi R, Cook GR. Tetrahedron Lett. 2007; 48: 7085
5b Choudhary VR, Jana SK, Patil NS, Bhargava SK. Microporous and Mesoporous Materials 2003; 57: 21
5c Bachari K, Cherifi O. J. Porous Mater. 2008; 15: 325

6 Duquenne C, Gillet J.-P, Kervennal J, Ruppin C, Vaultier M. WO Patent 067490, 2004 ; Chem. Abstr. 2004, 141, 140181
7 J. Ichikawa, presented in part at the 2012 Dasan Conference: Fluorine Chemistry to Environment and Health Aspects (FCEHA), The City7 Pullman Ambassador Hotel, Changwon, South Korea, November 14–16, 2012; Invited Lecture-03: Electrophilic Activation and Cyclization of Fluoro Alkenes Directed toward PAH Synthesis, page 51 of abstract book: 2012-Dasan Conference-Program Book-DSSHIN.pdf�.

8a Miyai T, Onishi Y, Baba A. Tetrahedron Lett. 1998; 39: 6291
8b Miyai T, Onishi Y, Baba A. Tetrahedron 1999; 55: 1017

9a For a recent review, see: Liu J, Obando D, Liao V, Lifa T, Codd R. Eur. J. Med. Chem. 2011; 46: 1949
9b Battilocchio C, Baxendale IR, Biava M, Kitching MO, Ley SV. Org. Process Res. Dev. 2012; 16: 798; and references cited therein

Adamantylphosphines:

10a Zapf A, Ehrentraut A, Beller M. Angew. Chem. Int. Ed. 2000; 39: 4153
10b Köllhofer A, Pullmann T, Plenio H. Angew. Chem. Int. Ed. 2003; 42: 1056
10c Ehrentraut A, Zapf A, Beller M. Adv. Synth. Catal. 2002; 344: 209
10d Neumann H, Brennführer A, Beller M. Chem. Eur. J. 2008; 14: 3645
10e Neumann H, Brennführer A, Beller M. Adv. Synth. Catal. 2008; 350: 2437
10f Wu X.-F, Neumann H, Beller M. Chem. Eur. J. 2010; 16: 9750

NHCs:

11a Arduengo AJ. III, Harlow RL, Kline M. J. Am. Chem. Soc. 1991; 113: 361
11b Dinger MB, Nieczypor P, Mol JC. Organometallics 2003; 22: 5291
11c Song JJ, Tan Z, Reeves JT, Fandrick DR, Yee NK, Senanayake CH. Org. Lett. 2008; 10: 877
11d Seo H, Roberts BP, Abboud KA, Merz KM. Jr, Hong S. Org. Lett. 2010; 12: 4860
11e Endo K, Grubbs RH. J. Am. Chem. Soc. 2011; 133: 8525
11f Keitz BK, Endo K, Patel PR, Herbert MB, Grubbs RH. J. Am. Chem. Soc. 2012; 134: 693

12a Boulch R, Scheurer A, Mosset P, Saalfrank RW. Tetrahedron Lett. 2000; 41: 1023
12b Clariana J, Comelles J, Moreno-Mañas M, Vallribera A. Tetrahedron: Asymmetry 2002; 13: 1551
12c Matsumura S, Maeda Y, Nishimura T, Uemura S. J. Am. Chem. Soc. 2003; 125: 8862
12d Busch M, Schlageter M, Weingand D. Chem. Eur. J. 2009; 15: 8251
12e Yang J, Wu S, Chen F.-X. Synlett 2010; 2725
12f Dong S, Liu X, Zhang Y, Lin L, Feng X. Org. Lett. 2011; 13: 5060
12g Beckendorf S, Mancheño OG. Synthesis 2012; 44: 2162

13a Dondoni A, Marra A. J. Org. Chem. 2006; 71: 7546
13b Nasr K, Pannier N, Frangioni JV, Maison W. J. Org. Chem. 2008; 73: 1056
13c Pannier N, Maison W. Eur. J. Org. Chem. 2008; 1278
13d Tominaga M, Masu H, Azumaya I. J. Org. Chem. 2009; 74: 8754
13e Humblet V, Misra P, Bhushan KR, Nasr K, Ko Y.-S, Tsukamoto T, Pannier N, Frangioni JV, Maison W. J. Med. Chem. 2009; 52: 544
13f Singh A, Tolev M, Schilling CI, Bräse S, Griesser H, Richert C. J. Org. Chem. 2012; 77: 2718
13g Grigg R, Elboray EE, Aly MF, Abbas-Temirek HH. Chem. Commun. 2012; 48: 11504

14 Newman H. Synthesis 1972; 692
15 Perkins R, Bennett S, Bowering E, Burke J, Reid K, Wall D. Chem. Ind. 1980; 790
16 Shortly before the report of the FeCl₃-catalyzed reaction, the reaction of 1-fluoroadamantane (very expensive, in contrast to 1, which is inexpensive) with benzene, toluene and bromobenzene under catalysis by PhPF₄ was reported, see: Weiß J.-V, Wray V, Schmutzler R. Z. Naturforsch. 1979; 34b: 1286. Furthermore, benzene was not reported to give 3a under these conditions but instead gave p-di(1-adamantyl)benzene. Toluene gave a mixture of meta and para isomers of mono(1-adamantyl)toluene
17 Olah GA, Farooq O, Farnia SM. F, Wu A.-h. J. Org. Chem. 1990; 55: 1516
18 Olah GA, Török B, Shamma T, Török M, Surya Prakash GK. Catal. Lett. 1996; 42: 5

19a Beregszászi T, Török B, Molnár Á, Olah GA, Surya Prakash GK. Catal. Lett. 1997; 48: 83
19b Török B, Molnár Á. Compt. Rend. Acad. Sci. Paris, Série IIc 1998; 381
19c Török B, Kiricsi I, Molnár Á, Olah GA. J. Catal. 2000; 193: 132

20 Using more InBr₃ than 0.05 equiv favored the formation of a small amount of the more polar 1,3-diphenyladamantane.
21 Indium mesylate and tosylate were prepared by dissolving metallic indium powder in aqueous methanesulfonic acid (3.2 equiv) or p-toluenesulfonic acid (3.0 equiv) at 70 °C (respectively 0.3 and 0.8 mL H₂O/mmol In was used) for respectively 2 and 20 h, followed by removal of water under vacuum at 70 °C. Remarkably, in contrast to indium mesylate and halides, indium tosylate did not exhibit appreciable hygroscopicity, a fact that made it far more convenient to handle.
22 Representative Procedure: InBr₃ (7.1 mg, 0.02 mmol) was introduced in an oven- or flame-dried 10 mL round-bottomed flask followed by an olive-shaped magnetic stirring bar. The apparatus was dried by heating for 1–2 min with a heat gun under vacuum. 1-Bromoadamantane (1; 86 mg, 0.4 mmol) and the monosubstituted benzene 2a–h (or benzene itself, 1 mL) were added. The flask was flushed under nitrogen and well stoppered.²⁶ The reaction was left under gentle stirring in a water or oil bath at the specified temperature (see Tables) with protection against light by aluminum foil. After reaction for the specified time (see Tables), abundant evolution of hydrogen bromide (white smoke, caution!) occurred on opening. The reaction mixture was taken up with pentane and washed with water until neutral. After drying (Na₂SO₄) and concentration, chromatography on silica gel (ca. 3 g), eluting with pentane, afforded monoadamantylated benzene 3a–h followed in some cases by more polar 1-bromo-3-aryladamantane (4) and 1,3-diaryladamantane (5). 1-Phenyladamantane (3a): Mp 82 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.37 (dm, J ~ 8 Hz, 2 H), 7.31 (ddm, J = 8.2, 6.8 Hz, 2 H), 7.17 (ddt, J = 7.6, 6.7, 1.4 Hz, 1 H), 2.12–2.07 (m, 3 H), 1.92 (d, J = 2.8 Hz, 6 H), 1.83–1.72 (m, 6 H). ¹³C NMR (100 MHz, CDCl₃): δ = 151.34 (1C_q), 128.10 (2CH), 125.50 (1CH), 124.84 (2CH), 43.23 (3CH₂), 36.88 (3CH₂), 36.22 (1C_q), 29.04 (3CH). 1-(4-Methylphenyl)adamantane (3b): Mp 97–98 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.26 (half of an A₂X₂ system, 2 H), 7.13 (half of an A₂X₂ system coupled with CH₃, J _{with Me} = 0.7 Hz, 2 H), 2.32 (t, J = 0.7 Hz, 3 H, CH ₃), 2.12–2.05 (m, 3 H), 1.90 (broad d, J = 2.8 Hz, 6 H), 1.82–1.71 (m, 6 H). ¹³C NMR (100 MHz, CDCl₃): δ = 148.48 (1C_q), 134.90 (1C_q), 128.81 (2CH), 124.72 (2CH), 43.30 (3CH₂), 36.87 (3CH₂), 35.85 (1C_q), 29.03 (3CH), 20.87 (1CH₃). 1-(4-Ethylphenyl)adamantane (3c): Mp 58 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.28 (half of an A₂X₂ system, 2 H), 7.15 (half of an A₂X₂ system coupled with CH₂, J _{with CH2} = 0.6 Hz, 2 H), 2.62 (q, J = 7.6 Hz, 2 H, CH ₂CH₃), 2.12–2.05 (m, 3 H), 1.91 (broad d, J = 2.8 Hz, 6 H), 1.82–1.71 (m, 6 H), 1.23 (t, J = 7.6 Hz, 3 H, CH₂CH ₃). ¹³C NMR (100 MHz, CDCl₃): δ = 148.68 (1C_q), 141.23 (1C_q), 127.55 (2CH), 124.75 (2CH), 43.29 (3CH₂), 36.87 (3CH₂), 35.88 (1C_q), 29.03 (3CH), 28.29 (1CH₂), 15.45 (1CH₃). 1-(4-Isopropylphenyl)adamantane (3d): Mp 87 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.28 (half of an A₂X₂ system, 2 H), 7.18 (half of an A₂X₂ system coupled with CH, J _{with CH} = 0.6 Hz, 2 H), 2.88 [qq, J = 6.9, 6.9 Hz, 1 H, CH(CH₃)₂], 2.12–2.05 (m, 3 H), 1.91 (broad d, J = 2.8 Hz, 6 H), 1.82–1.70 (m, 6 H), 1.24 [d, J = 6.9 Hz, 6 H, CH(CH ₃)₂]. ¹³C NMR (100 MHz, CDCl₃): δ = 148.74 (1C_q), 145.81 (1C_q), 126.09 (2CH), 124.69 (2CH), 43.29 (3CH₂), 36.88 (3CH₂), 35.87 (1C_q), 33.55 (1CH), 29.03 (3CH), 24.02 (2CH₃). 1-(4-Isobutylphenyl)adamantane (3e): Mp 34.5 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.25 (half of an A₂X₂ system, 2 H), 7.08 (half of an A₂X₂ system coupled with CH₂, J _{with CH2} = 0.6 Hz, 2 H), 2.44 (d, J = 7.2 Hz, 2 H, CH₂ of i-Bu), 2.12–2.05 (m, 3 H), 1.91 (broad d, J = 2.8 Hz, 6 H), 1.85 [tqq, J = 7.2, 6.6, 6.6 Hz, 1 H, CH(CH₃)₂], 1.82–1.70 (m, 6 H), 0.90 (d, J = 6.6 Hz, 6 H, CH(CH ₃)₂). ¹³C NMR (CDCl₃, 100 MHz): δ = 148.67 (1C_q), 138.70 (1C_q), 128.80 (2CH), 124.49 (2CH), 45.00 (CH₂), 43.30 (3CH₂), 36.89 (3CH₂), 35.88 (1C_q), 30.19 (1CH), 29.04 (3CH), 22.48 (2CH₃). Anal. Calcd for C₂₀H₂₈ (268.44): C, 89.49; H, 10.51. Found: C, 89.57; H, 10.46. 1-(4-tert-Butylphenyl)adamantane (3i): Mp 127.5 °C. ¹H NMR (CDCl₃, 400 MHz): δ = 7.34 (half of an A₂X₂ system, 2 H), 7.29 (half of an A₂X₂ system, 2 H), 2.12–2.05 (m, 3 H), 1.91 (d, J = 2.8 Hz, 6 H), 1.83–1.70 (m, 6 H), 1.31 [s, 9 H, C(CH ₃)₃]. ¹³C NMR (CDCl₃, 100 MHz): δ = 148.30 (1C_q), 148.06 (1C_q), 124.92 (2CH), 124.42 (2CH), 43.22 (3CH₂), 36.85 (3CH₂), 35.76 (1C_q), 34.25 (1C_q), 31.40 (3CH₃), 28.99 (3CH). 1,4-Di-1-adamantylbenzene (3j) ¹H NMR (400 MHz, CDCl₃): δ = 7.31 (s, 4 H), 2.12–2.05 (m, 6 H), 1.91 (d, J = 2.8 Hz, 12 H), 1.82–1.71 (m, 12 H). ¹³C NMR (100 MHz, CDCl₃): δ = 148.35 (2C_q), 124.45 (4CH), 43.21 (6CH₂), 36.86 (6CH₂), 35.79 (2C_q), 28.99 (6CH). For data of other compounds, see the Supporting Information.
23 For instance, no reaction was observed with 1 and isobutylbenzene at 40 °C in CCl₄. In 1,2-dichloroethane and 1-chlorobutane at 35–40 °C, the reactions of 1 with isobutylbenzene and tert-butylbenzene afforded complex mixtures.
24 Halobenzenes were not studied in CH₂Cl₂ as solvent because of their reduced reactivity and also due to the fact that InBr₃ was not a good catalyst in their case.
25 The same procedure as previously described was used, except that a reduced amount of aromatic substrate was used (see Table 3) and dichloromethane was added (its amount was adjusted by weight after flushing with nitrogen and stoppering).
26 Based on two experiments that were performed with toluene and ethylbenzene with HBr vented through a bubbler, no change was observed in reaction rate or selectivity (same para/meta ratios). Yields of 99% were obtained compared with 90 and 92% (InCl₃ as a catalyst).

Zusatzmaterial

Supporting Information