The Directed ortho Metalation (DoM)–Cross-Coupling Connection: Synthesis of Polyfunctional Biaryls

Dedicated to Scott Denmark, a man for all seasons in organic chemistry.

Published as part of the Special Section dedicated to Scott E. Denmark on the occasion of his 65^th birthday.

Abstract

A comparative evaluation of the combined directed ortho metalation (DoM)–Suzuki–Miyaura and DoM–Negishi cross-coupling reactions with aryl triflates for the synthesis of substituted biaryls is described. Both ortho-zinc and ortho-boron aryl directed metalation group (DMG = CON(i-Pr)₂, OCONEt₂, OMOM, NHBoc) substrates were evaluated. The superiority of the DoM–Negishi over the DoM–Suzuki–Miyaura reaction in operational convenience and mild reaction conditions is noted. Orthogonal Negishi and Suzuki–Miyaura with Corriu–Kumada reactions for the synthesis of a teraryl derivative is also reported.

Key words

Suzuki–Miyaura coupling - Negishi coupling - cross-coupling - directed ortho metalation

• References

• 1 Current address: Bristol-Myers Squibb Co., Department of Medicinal Chemistry, Princeton, NJ 08543-4000, USA.
• 2a Metal-Catalyzed Cross-Coupling Reactions and More . Vol. 1-3. de Meijere A, Bräse S, Oestreich M. Wiley-VCH; Weinheim: 2014
• 2b For a historical perspective, see: Johansson Seechurn CC. C, Kitching MO, Colacot TJ, Snieckus V. Angew. Chem. Int. Ed. 2012; 51: 5062
• 2c For applications in the pharmaceutical industry, see: Magano J, Dunetz JR. Chem. Rev. 2011; 111: 2177
• 3 Snieckus V. Chem. Rev. 1990; 90: 879
• 4a Macklin T, Snieckus V. In Handbook of C–H Transformations . Dyker G. Wiley-VCH; New York: 2005: 106
• 4b Hartung CG, Snieckus V. In Modern Arene Chemistry . Astruc D. Wiley-VCH; New York: 2002: 330
• 5 Haag B, Mosrin M, Ila H, Malakhov V, Knochel P. Angew. Chem. Int. Ed. 2011; 50: 9794
• 6a Sengupta S, Leite M, Raslan DS, Quesnelle C, Snieckus V. J. Org. Chem. 1992; 57: 4066
• 6b Antoft-Finch A, Blackburn T, Snieckus V. J. Am. Chem. Soc. 2009; 131: 17750
• 6c Quasdorf KW, Antoft-Finch A, Liu P, Silberstein AL, Komaromi A, Blackburn T, Ramgren SD, Houk KN, Snieckus V, Garg NK. J. Am. Chem. Soc. 2011; 133: 6352
• 7a Macklin TK, Snieckus V. Org. Lett. 2005; 7: 2519
• 7b Silberstein AL, Ramgren SD, Garg NK. Org. Lett. 2012; 14: 3796
• 8 Milburn RR, Snieckus V. Angew. Chem. Int. Ed. 2004; 43: 888
• 9a Cai X, Snieckus V. Org. Lett. 2004; 6: 2293
• 9b Alessi M, Larkin AL, Lai S, Ogilvie KA, Green LA, Lopes S, Snieckus V. J. Org. Chem. 2007; 72: 1588

For the use of indole-N-CONEt₂ in DoM and cross-coupling, see:
• 9c Hartung CG, Fecher A, Chapell B, Snieckus V. Org. Lett. 2003; 5: 1899
• 9d Zhao Z, Jaworski A, Piel I, Snieckus V. Org. Lett. 2008; 10: 2617
• 9e Zhao Z, Snieckus V. Org. Lett. 2005; 7: 2523
• 10 Evans PA, Nelson JD, Stanley AL. J. Org. Chem. 1995; 60: 2298
• 11a Brimble MA, Chan SH. Aust. J. Chem. 1998; 51: 235
• 11b Chamoin S, Houldsworth S, Snieckus V. Tetrahedron Lett. 1998; 39: 4175
• 11c Echavarren AM, Tamayo N, Cardenas DJ. J. Org. Chem. 1994; 59: 6075
• 11d Fu JM, Sharp MJ, Snieckus V. Tetrahedron Lett. 1988; 29: 5459
• 12 Seganish WM, DeShong P. J. Org. Chem. 2004; 69: 6790
• 13 Monzon G, Knochel P. Synlett 2010; 304
• 14a Rohbogner CJ, Wunderlich SH, Clososki GC, Knochel P. Eur. J. Org. Chem. 2009; 1781
• 14b Wunderlich SH, Rohbogner CJ, Unsinn A, Knochel P. Org. Process Res. Dev. 2010; 14: 339
• 14c Clososki GC, Rohbogner CJ, Knochel P. Angew. Chem. Int. Ed. 2007; 46: 7681
• 14d See also ref. 13
• 15a Ghosh S, Kumar AS, Mehta GN, Soundararajan R, Sen S. J. Chem. Res. 2009; 205
• 15b Bologna A, Barreca G, Allegrini P. Eur. Pat. Appl. EP 1878735, 2008 ; Chem. Abstr. 2008, 148, 144870
• 16a Fu Y, Laurent S, Muller RN. Eur. J. Org. Chem. 2002; 3966
• 16b Akine S, Nagumo H, Nabeshima T. Dalton Trans. 2013; 42: 15974
• 17a Hatakeyama T. PCT Int. Appl. WO 2016143819, 2016 ; Chem. Abstr. 2016, 165, 406046
• 17b Numano M, Nagami N, Nakatsuka S, Katayama T, Nakajima K, Tatsumi S, Yasuda N, Hatakeyama T. Chem. Eur. J. 2016; 22: 11574
• 17c Bryan ZJ, McNeil AJ. Chem. Sci. 2013; 4: 1620
• 17d Handa S, Arachchige YL. N. M, Slaughter LM. J. Org. Chem. 2013; 78: 5694
• 18a Jaric M, Haag BA, Unsinn A, Karaghiosoff K, Knochel P. Angew. Chem. Int. Ed. 2010; 49: 5451
• 18b McCann LC, Organ MG. Angew. Chem. Int. Ed. 2014; 53: 4386
• 19a Domini CE, Silbestri GF, Fernández Band B, Chopa AB. Ultrason. Sonochem. 2012; 19: 410
• 19b Chopa AB, Silbestri GF, Lockhart MT. J. Organomet. Chem. 2005; 690: 3865
• 19c Prasad AS, Satyanarayana B. Bull. Korean Chem. Soc. 2012; 33: 2789
• 19d Lee D.-H, Qian Y, Park J.-H, Lee J.-S, Shim S.-E, Jin M.-J. Adv. Synth. Catal. 2013; 355: 1729
• 20a Abe H, Hashikawa D, Minami T, Ohtani K, Masuda K, Matsumoto S, Inouye M. J. Org. Chem. 2018; 83: 3132
• 20b Kakuta H, Yamada S, Watanabe M. PCT Int. Appl. WO 2017094838, 2017 ; Chem. Abstr. 2017, 167, 68445.
• 20c Stanetty P, Koller H, Mihovilovic M. J. Org. Chem. 1992; 57: 6833
• 21 See also ref. 9e.
• 22 Griffen EJ, Roe DG, Snieckus V. J. Org. Chem. 1995; 60: 1484
• 23 Blackburn T. M.Sc. Thesis. Queen’s University; Canada: 2009
• 24 Rohbogner CJ, Wirth S, Knochel P. Org. Lett. 2010; 12: 1984
• 25 Rohbogner CJ, Clososki GC, Knochel P. Angew. Chem. Int. Ed. 2008; 47: 1503
• 26a Siddiqui MA, Snieckus V. Tetrahedron Lett. 1988; 29: 5463
• 26b Lavrard H, Popowycz F. Eur. J. Org. Chem. 2017; 600
• 26c Ishida T, Ikota H, Kurahashi K, Tsukano C, Takemoto Y. Angew. Chem. Int. Ed. 2013; 52: 10204
• 26d Holzapfel CW, Dwyer C. Heterocycles 1998; 48: 1513

For indole-N-Boc DoM and cross-coupling, see:
• 26e Sakamoto T, Kondo Y, Takazawa N, Yamanaka H. J. Chem. Soc., Perkin Trans. 1 1996; 1927
• 27a Durban MM, Kazarinoff PD, Segawa Y, Luscombe CK. Macromolecules 2011; 44: 4721
• 27b Peterson MA, Nilsson BL. Synth. Commun. 1999; 29: 3821
• 27c Pascal C, Dubois J, Guenard D, Tchertanov L, Thoret S, Gueritte F. Tetrahedron 1998; 54: 14737
• 27d Iwao M, Takehara H, Obta S, Watanabe M. Heterocycles 1994; 38: 1717
• 27e See also ref. 26d
• 28a MacNeil S, Familoni OB, Snieckus V. J. Org. Chem. 2001; 66: 3662
• 28b Schneider C, Broda E, Snieckus V. Org. Lett. 2011; 13: 3588
• 28c See also ref. 9e
• 29a Iwao M, Iihama T, Mahalanabis KK, Perrier H, Snieckus V. J. Org. Chem. 1989; 54: 24
• 29b Bacani GM, Eccles W, Fitzgerald AE, Goldberg SD, Hack MD, Hawryluk NA, Jones WM, Keith JM, Krawczuk P, Lebsack AD, Lee-Dutra A, Liu J, Mcclure KJ, Meduna SP, Pippel DJ, Rosen MD, Sales ZS. PCT Int. Appl. WO 2014121055, 2014 ; Chem. Abstr. 2014, 161, 336411
• 30 For Negishi couplings of ortho-halo sulfones not derived by DoM, see: Jones RM, Han S, Moody JV. PCT Int. Appl. WO 2009151626, 2009 ; Chem. Abstr. 2009, 152, 57322
• 31 For ortho-bromo sulfones not derived by DoM, see: Iwama S, Tanaka T, Gotoh N. PCT Int. Appl. WO 2011145669, 2011 ; Chem. Abstr. 2011, 155, 683708

For the original DoM of phosphines, see:
• 32a Schaub B, Jenny T, Schlosser M. Tetrahedron Lett. 1984; 25: 4097

For DoM and Ullmann coupling, see:
• 32b Brown JM, Woodward S. J. Org. Chem. 1991; 56: 6803

For indole-N-PO(t-Bu)₂ DoM and cross-coupling, see ref. 9c. For S-M coupling of ortho-bromo phosphine oxides which, in theory, may be derived by DoM, see for example:
• 32c Joshaghani M, Faramarzi E, Rafiee E, Daryanavard M, Xiao J, Baillie C. J. Mol. Catal. A: Chem. 2007; 273: 310
• 32d Baillie C, Chen W, Xiao J. Tetrahedron Lett. 2001; 42: 9085
• 33 Yamamoto T, Suginome M. Angew. Chem. Int. Ed. 2009; 48: 539
• 34a Dubost E, Magnelli R, Cailly T, Legay R, Fabis F, Rault S. Tetrahedron 2010; 66: 5008
• 34b Chołuj A, Kula P, Dąbrowski R, Tykarska M, Jaroszewicz L. J. Mat. Chem. C 2014; 2: 891
• 34c Park MS, Park HJ, Kim OY, Lee JY. Org. Electron. 2013; 14: 1504
• 35 Wang J, Meng G, Xie K, Li L, Sun H, Huang Z. ACS Catal. 2017; 7: 7421
• 36 For chlorothiophene metalation and cross-coupling, see: Kunz T, Knochel P. Chem. Eur. J. 2011; 17: 866
• 37a Saa JM, Martorell G. J. Org. Chem. 1993; 58: 1963
• 37b Farina V, Krishnamurthy V, Scott WJ. Org. React. (N. Y.) 1997; 50: 1
• 38 Sharp MJ, Snieckus V. Tetrahedron Lett. 1985; 26: 5997
• 39 Sharp MJ, Cheng W, Snieckus V. Tetrahedron Lett. 1987; 28: 5093
• 40 Guillier F, Nivoliers F, Godard A, Marsias F, Queguiner G, Siddiqui MA, Snieckus V. J. Org. Chem. 1995; 60: 292
• 41 For a review, see: Whisler MC, MacNeil S, Snieckus V, Beak P. Angew. Chem. Int. Ed. 2004; 43: 2206
• 42a For the most recent studies, see: Jørgensen KB, Rantanen T, Dörfler T, Snieckus V. J. Org. Chem. 2015; 80: 9410
• 42b For natural products synthesis, see: Wang X, Fu J.-m, Snieckus V. Helv. Chim. Acta 2012; 95: 2680
• 43 Fu J.-m, Zhao B.-p, Sharp MJ, Snieckus V. J. Org. Chem. 1991; 56: 1683
• 44 For the original study, see: Alo BI, Kandil A, Patil PA, Sharp MJ, Siddiqui MA, Josephy PD, Snieckus V. J. Org. Chem. 1991; 56: 3763
• 45 For application to natural products synthesis, see: James C, Snieckus V. J. Org. Chem. 2009; 74: 4080
• 46 For a comparison of Negishi and S-M couplings, see: Brandao MA. F, de Oliviera AB, Snieckus V. Tetrahedron Lett. 1993; 34: 2437
• 47 For a review, see: Board J, Cosman J, Rantanen T, Singh S, Snieckus V. Platinum Met. Rev. 2013; 57: 234
• 48 Macklin T, Ang P, Blanchet J, Metallinos C, Snieckus V. J. Org. Chem. 2007; 72: 3199
• 49 Cheng W, Snieckus V. Tetrahedron Lett. 1987; 28: 5097
• 50 Vogler M, Koert U, Dorsch D, Gleitz J, Raddatz P. Synlett 2003; 1683
• 51 Takeda K, Terauchi T, Hashizume M, Shin K, Ino M, Shibata H, Yonaga M. Bioorg. Med. Chem. Lett. 2012; 22: 5372
• 52 Larsen RD, King AO, Chen CY, Corley EG, Foster BS, Roberts FE, Yang C, Lieberman DR, Reamer RA, Tschaen DM, Verhoeven TR, Reider PJ, Lo YS, Rossano LuT, Brookes As, Meloni D, Moore JR, Arnett JF. J. Org. Chem. 1994; 59: 6391
• 53 Gosselin F, Lau S, Nadeau C, Trinh T, O’Shea PD, Davies IW. J. Org. Chem. 2009; 74: 7790
• 54 Agharahimi MR, LeBel NA. J. Org. Chem. 1995; 60: 1856
• 55 Benesch L, Bury P, Guillaneux D, Houldsworth S, Wang X, Snieckus V. Tetrahedron Lett. 1998; 39: 961
• 56 Hird M, Toyne KJ. J. Mater. Chem. 1995; 5: 2239
• 57 Rice JE, Cai Z.-W, He Z.-M, LaVoie EJ. J. Org. Chem. 1995; 60: 8101
• 58 See accompanying manuscript: Quesnelle CA, Snieckus V. Synthesis 2018; 50
• 59 Quesnelle CA, Familoni OB, Snieckus V. Synlett 1994; 349

We chose triflate coupling partners in view of their high reactivity; see:
• 60a Fu J.-m, Snieckus V. Tetrahedron Lett. 1990; 31: 1665
• 60b Oh-e T, Miyaura N, Suzuki A. J. Org. Chem. 1993; 58: 2201

For clever use of the inherent selectivity of aryl bromides and aryl triflates, see:
• 60c Ackerman LK. G, Lovel MM, Weix DJ. Nature 2015; 524: 454

For recent comprehensive studies of O-aryl carbamate DoM chemistry, see:
• 61a Miah MA. J, Sibi MP, Chattopadhyay S, Familoni OB, Snieckus V. Eur. J. Org. Chem. 2018; 440
• 61b Miah MA. J, Sibi MP, Chattopadhyay S, Familoni OB, Snieckus V. Eur. J. Org. Chem. 2018; 447
• 62 Additional examples of similar Negishi coupling reactions of aryl triflates are given in our original disclosure; see ref. 59.
• 63 Miyaura N, Suzuki A. Chem. Rev. 1995; 95: 2457

For sterically demanding S-M reactions, see:
• 64a Fu J.-m, Snieckus V. Can. J. Chem. 2000; 78: 905

For comprehensive studies of steric effects, see:
• 64b Yin J, Rainka MP, Zhang X.-X, Buchwald SL. J. Am. Chem. Soc. 2002; 124: 1162
• 64c Raders SM, Moore JN, Parks JK, Miller AD, Leißing TM, Kelley SP, Rogers RD, Shaughnessy KH. J. Org. Chem. 2013; 78: 4649
• 65 Quesnelle, C. A., unpublished results.
• 66a Rottländer M, Palmer N, Knochel P. Synlett 1996; 573
• 66b See also ref. 5
• 67 Koch K, Chambers RJ, Biggers MS. Synlett 1994; 347
• 68 Cosmini C, Corpet M. In Cross Coupling and Heck-Type Reactions 1, Science of Synthesis . Molander GA. Thieme; Stuttgart: 2013: 623
• 69 Still WC, Kahn M, Mitra A. J. Org. Chem. 1978; 43: 2923
• 70 Perrin DD, Armarego WL, Perrin DR. Purification of Laboratory Chemicals . Pergamon Press; Oxford: 1980. 2nd ed.
• 71 Watson SC, Eastham JF. J. Organomet. Chem. 1967; 9: 165
• 72 Coulson DR. Inorg. Synth. 1972; 13: 121
• 73 Subramanian LR, Hanack M, Chang LW. K, Imhoff MA, Schleyer P. vR, Effenberger F, Kurtz W, Stang PJ, Dueber TE. J. Org. Chem. 1976; 41: 4099
• 74 Scott WJ, Crisp GT, Stille JK. Org. Synth. 1990; 68: 116
• 75 Batcho AD, Leimgruber W. Org. Synth. 1985; 63: 214
• 76 Wang SY. J. Am. Chem. Soc. 1959; 81: 3786
• 77 See (mp data not given): Hirota K, Kitade Y, Isobe Y, Maki Y. Heterocycles 1987; 26: 355
• 78 Stang P, Anderson AG. J. Org. Chem. 1976; 41: 781
• 79 Stang PJ, Treptow WL. J. Med. Chem. 1981; 24: 468
• 80 Cabri W, Candiani I, Bedeschi A, Penco S, Santi R. J. Org. Chem. 1992; 57: 1481
• 81 Hendrickson JB, Bergeron R. Tetrahedron Lett. 1973; 4607
• 82 Echavarren AM, Stille JK. J. Am. Chem. Soc. 1987; 109: 5478
• 83 Fu J.-m. Ph.D. Thesis. University of Waterloo; Canada: 1990
• 84 Sharp MJ. M.Sc. Thesis. University of Waterloo; Canada: 1986