Air-Stable Diaminophosphine Sulfides as Preligands for Nickel-Catalyzed Cross-Couplings of Unactivated Fluoro(hetero)arenes

Abstract

Air-stable secondary diaminophosphine sulfide preligands enable challenging nickel-catalyzed cross-coupling reactions of electron-deficient as well as electron-rich fluoro(hetero)arenes as electrophiles.

Key words

fluoroarenes - Grignard reagents - ligands - nickel - secondary phosphine sulfide

References and Notes

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• For recent representative studies on catalyzed functionali-zations of C-F bonds with metals other than nickel, see:
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• 13 Littke AF. In Modern Arylation Methods   Ackermann L. Wiley-VCH; Weinheim: 2009.  p.25 
• For examples of nickel-catalyzed cross-coupling reactions between aryl fluorides and boronic acids, see:
• 14a Schaub T. Backes M. Radius U. J. Am. Chem. Soc.  2006,  128:  15964 
• 14b See also: Schaub T. Fischer P. Steffen A. Braun T. Radius U. Mix A. J. Am. Chem. Soc.  2008,  130:  9304 
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• 16 Ackermann L. Synlett  2007,  507 
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• Representative examples of HASPO preligands in catalyzed cross-coupling chemistry from our laboratories:
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• 23 For an example of a secondary phosphine sulfide preligand in a cross-coupling of aryl chlorides, see: Li GW. Marshall WJ. Organometallics  2002,  21:  590 

24

Synthesis of 1,3-Bis-(2,6-diisopropylphenyl)[1,3,2]-diazaphospholane-2-sulfide (2)
1,3-Bis-(2,6-diisopropylphenyl)[1,3,2]diazaphospholane-2 oxide (3.06 g, 7.17 mmol) and Lawesson’s reagent (2.90 g, 7.17 mmol) were stirred in PhMe (25 mL) for 3 h at 110 ˚C. At ambient temperature, the reaction mixture was filtered, and the solvent was removed in vacuo. The remaining residue was purified by column chromatography (n-hexane-EtOAC = 4:1) to yield 2 (2.40 g, 76%) as a colorless solid (mp 189-191 ˚C). ^¹H NMR (300 MHz, CDCl₃): δ = 8.65 (d, J = 562.5 Hz, 1 H), 7.31 (t, J = 7.3 Hz, 2 H), 7.21 (dd, J = 7.7, 1.6 Hz, 2 H), 7.16-7.04 (m, 2 H), 3.67 (sept, J = 6.9 Hz, 6 H), 3.29 (sept, J = 6.7 Hz, 2 H), 1.37 (d, J = 6.7 Hz, 6 H), 1.32 (d, J = 7.1 Hz, 6 H), 1.29 (d, J = 7.5 Hz, 6 H), 1.28 (d, J = 7.1 Hz, 6 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 150.2 (C_q), 148.8 (C_q), 133.4 (C_q, J = 5.0 Hz), 128.4 (CH), 124.7 (CH), 123.8 (CH), 50.4 (CH₂), 50.3 (CH₂), 29.1 (CH), 28.8 (CH), 25.8 (CH₃), 25.0 (CH₃), 24.8 (CH₃), 24.4 (CH₃). ^³¹P NMR (121 MHz, CDCl₃): δ = 47.65. IR (KBr): 2962, 2926, 2867, 2306, 1464, 1448, 1382, 1323, 1261, 1086, 984, 762 cm^-¹. MS (EI): m/z (%) = 442 (2) [M⁺], 409 (100), 221 (2), 191 (13), 160 (3), 132 (4), 43 (6). ESI-HRMS: m/z calcd for C₂₆H₄₀N₂PS [M + H⁺]: 443.2650; found: 443.2644.

25

Synthesis of 5a (Table 1, Entry 9); Typical Procedure
[Ni(acac)₂] (7 mg, 0.03 mmol, 3.0 mol%) and 2 (13 mg, 0.03 mmol, 3.0 mol%) were stirred in THF (2.0 mL) for 10 min at ambient temperature under N₂. Compound 3d (126 mg, 1.00 mmol) was added, and the solution was stirred for additional 5 min. Thereafter, 4d (1.75 M in THF, 0.85 mL, 1.50 mmol) was added, and the resulting solution was stirred for 21 h at ambient temperature. EtOAc (75 mL) and H₂O (75 mL) were added, and the separated aqueous phase was extracted with EtOAc (2 × 75 mL). The combined organic layers were dried over MgSO₄ and concentrated in vacuo. The remaining residue was purified by column chromatog-raphy on silica gel (n-hexane-EtOAc, 300:1 → 200:1 → 150:1 → 100:1) to yield 5a (160 mg, 87%) as a colorless solid (mp 88-89 ˚C). ^¹H NMR (300 MHz, CDCl₃): δ = 7.61-7.51 (m, 4 H), 7.40 (md, J = 8.1 Hz, 2 H), 7.3 (d, J = 7.4 Hz, 1 H), 6.96 (md, J = 8.9 Hz, 2 H), 3.87 (s, 3 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 159.1 (C_q), 140.8 (C_q), 133.7 (C_q), 128.7 (CH), 128.1 (CH), 126.7 (CH), 126.6 (CH), 114.2 (CH), 55.3 (OCH₃). IR (KBr): 2929, 2839, 1611, 1519, 1487, 1044, 836, 571, 438, 411 cm^-¹. MS (EI): m/z (%) = 184 (100) [M⁺], 169 (35), 141 (24), 115 (12), 92 (2), 76 (2), 63 (2). ESI-HRMS: m/z calcd for C₁₃H₁₂O: 184.0888; found: 184.0881. The spectral data are in accordance with those reported in the literature.^²0

26

Analytical Data
2-Methyl-6-(4-methoxyphenyl)quinoline (5n)
Mp 117-118 ˚C. ^¹H NMR (300 MHz, CDCl₃): δ = 8.04 (d, J = 8.3 Hz, 2 H), 7.93-7.34 (m, 2 H), 7.63 (md, J = 8.9 Hz, 2 H), 7.26 (d, J = 8.5 Hz, 1 H), 7.00 (md, J = 8.9 Hz, 2 H), 3.84 (s, 3 H), 2.73 (s, 3 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 159.3 (C_q), 158.6 (C_q), 147.0 (C_q), 138.0 (C_q), 136.2 (CH), 132.9 (C_q), 128.9 (CH), 128.9 (CH), 128.3 (C_q), 126.7 (CH), 124.4 (CH), 122.3 (CH), 114.3 (CH), 55.3 (OCH₃), 25.3 (CH₃). IR (KBr): 2964, 2925, 1599, 1521, 1492, 1285, 1260, 1243, 1191, 1036, 829 cm^-¹. MS (EI): m/z (%) = 249 (100) [M⁺], 234 (36), 206 (30), 124 (6), 103 (5), 51 (2). ESI-HRMS: m/z calcd for C₁₇H₁₆NO [M + H⁺]: 250.1232; found: 250.1226.


2-Methyl-6-(4-methylphenyl)quinoline (5o)
Mp 120-121 ˚C. ^¹H NMR (300 MHz, CDCl₃): δ = 8.10-8.02 (m, 2 H), 7.96-7.88 (m, 2 H), 7.59 (md, J = 8.2 Hz, 2 H), 7.27 (md, J = 8.4 Hz, 3 H), 2.74 (s, 3 H), 2.40 (s, 3 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 158.8 (C_q), 147.1 (C_q), 138.3 (C_q), 137.5 (C_q), 137.3 (C_q), 136.2 (CH), 129.6 (CH), 129.0 (CH), 128.9 (CH), 127.1 (CH), 126.6 (C_q), 124.8 (CH), 122.3 (CH), 25.4 (CH₃), 21.1 (CH₃). IR (KBr): 2917, 2854, 1619, 1598, 1563, 1518, 1492, 1391, 1313, 1013, 892, 816 cm^-¹. MS (EI): m/z (%) = 233 (100) [M⁺], 217 (3), 189 (2), 116 (4). ESI-HRMS: m/z calcd for C₁₇H₁₆N [M + H⁺]: 234.1282; found: 234.1277.
2-Methyl-6-(2-methylphenyl)quinoline (5p)
^¹H NMR (300 MHz, CDCl₃): δ = 8.03 (d, J = 7.7 Hz, 2 H), 7.71-7.58 (m, 2 H), 7.34-7.21 (m, 5 H), 2.76 (s, 3 H), 2.29 (s, 3 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 158.9 (C_q), 146.8 (C_q), 141.2 (C_q), 139.4 (C_q), 136.2 (CH), 135.5 (C_q), 131.2 (CH), 130.4 (CH), 129.9 (CH), 128.1 (CH), 127.5 (CH), 127.3 (CH), 126.2 (C_q), 125.8 (CH), 122.2 (CH), 25.4 (CH₃), 20.5 (CH₃). IR (KBr): 2952, 2920, 1600, 1561, 1487, 1454, 1373, 1312, 841, 815, 757, 726 cm^-¹. MS (EI): m/z (%) = 233 (100) [M⁺], 218 (11), 189 (6), 165 (3), 115 (6), 91 (2), 63 (2). ESI-HRMS: m/z calcd for C₁₇H₁₆N [M + H⁺]: 234.1277; found: 234.1281.
2-Methyl-6-(2,4,6-trimethylphenyl)quinoline (5q)
^¹H NMR (300 MHz, CDCl₃): δ = 8.04 (d, J = 9.1 Hz, 1 H), 8.02 (d, J = 8.7 Hz, 1 H), 7.52 (d, J = 1.8 Hz, 1 H), 7.45 (dd, J = 8.4, 1.8 Hz, 1 H), 7.29 (d, J = 8.4 Hz, 1 H), 6.96 (s, 2 H), 2.76 (s, 3 H), 2.31 (s, 3 H), 2.00 (s, 6 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 158.8 (C_q), 146.8 (C_q), 138.6 (C_q), 138.2 (C_q), 136.9 (C_q), 136.1 (C_q), 136.0 (CH), 131.5 (CH), 128.6 (CH), 128.1 (CH), 127.4 (CH), 126.5 (C_q), 122.1 (CH), 25.3 (CH₃), 21.0 (CH₃), 20.8 (CH₃). IR (KBr): 2949, 2917, 2856, 1599, 1563, 1483, 1375, 1309, 1259, 1221, 842, 812 cm^-¹. MS (EI): m/z (%) = 261 (100) [M⁺], 246 (42), 231 (9), 143 (83), 128 (10), 115 (13), 85 (23), 57 (26), 43 (33). ESI-HRMS: m/z calcd C₁₉H₂₀N [M + H⁺]: 262.1595; found: 262.1590.