Versatile Suzuki-Miyaura Coupling Reaction Using Diphenylvinylphosphine Ligands

Abstract

The scope of the utility of diphenylvinylphosphine ligands has been extended to include the Suzuki-Miyaura coupling reaction. A catalyst composed of phosphines and palladium efficiently mediates the reactions of a variety of aryl halides with arylboronic acids to afford the corresponding biphenyls in good to excellent yields.

Key words

cross-coupling - palladium - ligands - biaryls - halides

References and Notes

• 1a Miyaura N. Suzuki A. Chem. Rev.  1995,  95:  2457 
• 1b Miyaura N. Top. Curr. Chem.  2002,  219:  11 
• 2a Littke AF. Fu GC. Angew. Chem. Int. Ed.  2002,  41:  4176 
• 2b Rataboul F. Zapf A. Jackstell R. Harkal S. Riermeier T. Monsees A. Dingerdissen U. Beller M. Chem. Eur. J.  2004,  10:  2983 
• 3a Li GY. Angew. Chem. Int. Ed.  2001,  40:  1513 
• 3b Bei X. Crevier T. Guram AS. Jandeleit B. Powers TS. Turner HW. Uno T. Weinberg WH. Tetrahedron Lett.  1999,  40:  3855 
• 3c Feuerstein M. Doucet H. Santelli M. Tetrahedron Lett.  2001,  42:  5659 
• 3d Feuerstein M. Berthiol F. Doucet H. Santelli M. Synlett  2002,  1807 
• 3e Urgaonkar S. Nagarajan M. Verkade JG. Tetrahedron Lett.  2002,  43:  8921 
• 3f Kingston JV. Verkade JG. J. Org. Chem.  2007,  72:  2816 
• 3g Jensen JF. Johannsen M. Org. Lett.  2003,  5:  3025 
• 3h Colacot TJ. Shea HA. Org. Lett.  2004,  6:  3731 
• 3i Brenstrum T. Clattenburg J. Britten J. Zavorine S. Dyckx J. Robertson AJ. McNulty J. Capretta A. Org. Lett.  2006,  8:  103 
• 3j So CM. Lau CP. Kwong FY. Org. Lett.  2007,  9:  2795 
• 4a Littke AF. Fu GC. Angew. Chem. Int. Ed.  1998,  37:  3387 
• 4b Littke AF. Dai C. Fu GC. J. Am. Chem. Soc.  2000,  122:  4020 
• 4c Liu S.-Y. Choi MJ. Fu GC. Chem. Commun.  2001,  2408 
• 5a Zapf A. Ehrentraut A. Beller M. Angew. Chem. Int. Ed.  2000,  39:  4153 
• 5b Zapf A. Jackstell R. Rataboul F. Riermeier T. Monsees A. Fuhrmann C. Shaikh N. Dingerdissen U. Beller M. Chem. Commun.  2004,  38 
• 6a Nguyen HN. Huang X. Buchwald SL. J. Am. Chem. Soc.  2003,  125:  11818 
• 6b Walker SD. Barder TE. Martinelli JR. Buchwald SL. Angew. Chem. Int. Ed.  2004,  43:  1871 
• 6c Barder TE. Walker SD. Martinelli JR. Buchwald SL. J. Am. Chem. Soc.  2005,  127:  4685 
• 7a Kataoka N. Shelby S. Stambuli JP. Hartwig JF. J. Org. Chem.  2002,  67:  5553 
• 7b Stambuli JP. Kuwano R. Hartwig JF. Angew. Chem. Int. Ed.  2002,  41:  4746 
• 8a Dai C. Fu GC. J. Am. Chem. Soc.  2001,  123:  2719 
• 8b Buchwald SL. Mauger C. Mignani G. Scholz U. Adv. Synth. Catal.  2006,  348:  23 
• 8c Chinchilla R. Nájera C. Chem. Rev.  2007,  107:  874 
• 9 Suzuki K. Hori Y. Nishikawa T. Kobayashi T. Adv. Synth. Catal.  2007,  349:  2089 

10

For the preparation of 1b and 1c, see ref. 9.
Representative Procedure for the Preparation of 1a: A solution of 2-bromo-1,1-diphenylpropene⁹ (25.0 g, 91.5 mmol) and magnesium turnings (2.35 g, 96.1 mmol) in THF (100 mL) was stirred at r.t. under a nitrogen atmosphere. After addition of a piece of iodine, the solution was refluxed for 2 h. Then chlorodiisopropylphosphine (16.8 g, 109.8 mmol) was added dropwise at the same temperature and the mixed solution was refluxed for 18 h. After cooling to r.t., H₂O was added to the solution and the organic phase was extracted with toluene. The extract was dried over anhyd MgSO₄ and concentrated under reduced pressure. The concentrate was purified by recrystallization from MeOH (100 mL) to give the title compound (18.8 g, 66%) as a white solid. ¹H NMR (300 MHz, CDCl₃): δ = 1.07 (dd, J = 2.0, 7.1 Hz, 6 H), 1.12 (dd, J = 5.7, 6.3 Hz, 6 H), 1.80-2.04 (m, 2 H), 1.86 (d, J = 2.1 Hz, 3 H), 7.08-7.33 (m, 10 H). ¹³C NMR (75 MHz, CDCl₃): δ = 17.2 (d, J = 4.6 Hz), 20.8 (d, J = 1.1 Hz), 21.0 (d, J = 8.0 Hz), 24.4 (d, J = 14.3 Hz), 126.4, 126.5, 127.5, 128.1, 128.6, 130.2 (d, J = 3.5 Hz), 133.4 (d, J = 21.8 Hz), 143.5 (d, J = 8.6 Hz), 143.9 (d, J = 10.3 Hz), 155.3 (d, J = 32.0 Hz). ³¹P NMR (121 MHz, CDCl₃): δ = 5.44. HRMS (ESI): m/z [M + H]⁺ calcd for C₂₁H₂₇P: 311.1929; found: 311.1916.

11

Ligands 1a-c are solids stable enough to moisture and oxidation by molecular oxygen that they could be to be handled under air.

12

Typical Procedure for the Coupling Reaction: Aryl halide (1.0 equiv) and arylboronic acid (1.2 equiv) were added to a solution of KF (2.0 equiv), Pd(OAc)₂ (1.0 mol%) and ligand (2.0 mol%) in toluene (0.5 M) at r.t. under a nitrogen atmosphere. The solution was stirred at 80 °C for 1-3 h. After cooling to r.t., the solution was diluted with toluene, washed with H₂O and brine, dried over anhyd MgSO₄ and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography to give the coupling products. 4-Methoxybiphenyl (Table 1, entry 1): ¹H NMR (200 MHz, CDCl₃): δ = 3.85 (s, 3 H), 7.04-6.93 (m, 2 H), 7.60-7.23 (m, 7 H). ¹³C NMR (50 MHz, CDCl₃): δ = 55.3, 114.2, 126.6, 126.7, 128.1, 128.7, 133.8, 140.8, 159.1.