Strategies towards Chemoselective Suzuki–Miyaura Cross-Coupling

Abstract

Chemoselective Suzuki–Miyaura cross-coupling has emerged as a powerful method for the rapid preparation of sp²- and sp³-hybridized carbon frameworks based on control of the oxidative addition or transmetalation events. The field of chemoselective transmetalation has recently seen considerable development with several different strategies emerging including protected boronic acids, neighboring-group activation, and chemoselective speciation. Herein, these state-of-the-art approaches towards chemoselective Suzuki–Miyaura cross-coupling are highlighted.

1 Chemoselective Suzuki–Miyaura Cross-Coupling via Control of Oxidative Addition

2 Chemoselective Suzuki–Miyaura Cross-Coupling via Control of Transmetalation

3 Development and Use of BMIDA Reagents

4 Development and Use of BDAN Reagents

5 Use of Vicinal and Geminal Diboron Species in Chemoselective Cross-Coupling

6 Controlling Boron Solution Speciation

7 Summary

Key words

boron - catalysis - chemoselectivity - cross-coupling - palladium

• References

• 1a Cooper TW. J, Campbell IB, Macdonald SJ. F. Angew. Chem. Int. Ed. 2010; 49: 8082
• 1b Torborg C, Beller M. Adv. Synth. Catal. 2009; 351: 3027
• 2 Miyaura N, Yamada K, Suzuki A. Tetrahedron Lett. 1979; 36: 3437
• 3a Miyaura N, Suzuki A. Chem. Rev. 1995; 95: 2457
• 3b Lennox AJ. J, Lloyd-Jones GC. Chem. Soc. Rev. 2014; 43: 412
• 3c Lennox AJ. J, Lloyd-Jones GC. Angew. Chem. Int. Ed. 2013; 52: 7362
• 4 Martin R, Buchwald SL. Acc. Chem. Res. 2008; 41: 1461

For recent examples, see:
• 5a Molander GA, Sandrock DL. J. Am. Chem. Soc. 2008; 130: 15792
• 5b Tobisu M, Chatani N. Angew. Chem. Int. Ed. 2009; 48: 3565
• 5c Xu L, Ding S, Li P. Angew. Chem. Int. Ed. 2014; 53: 1822
• 5d Xu L, Li P. Synlett 2014; 25: 1799
• 6 Littke AF, Dai C, Fu GC. J. Am. Chem. Soc. 2000; 122: 4020
• 7 Sinclair DJ, Sherburn MS. J. Org. Chem. 2005; 70: 3730
• 8 Mancilla T, Contreras R, Wrackmeyer B. J. Organomet. Chem. 1986; 307: 1
• 9 Gillis EP, Burke MD. Aldrichimica Acta 2009; 42: 17
• 10 Gillis EP, Burke MD. J. Am. Chem. Soc. 2008; 130: 14084
• 11 Knapp DM, Gillis EP, Burke MD. J. Am. Chem. Soc. 2009; 131: 6961
• 12 Dick GR, Woerly EM, Burke MD. Angew. Chem. Int. Ed. 2012; 51: 2667
• 13 Woerly EM, Roy J, Burke MD. Nat. Chem. 2014; 6: 484
• 14 Lee SJ, Gray KC, Paek JS, Burke MD. J. Am. Chem. Soc. 2008; 130: 466
• 15 Noguchi H, Hojo K, Suginome M. J. Am. Chem. Soc. 2007; 129: 758
• 16 Noguchi H, Shioda T, Chou C, Suginome M. Org. Lett. 2008; 10: 377
• 17 Iwadate N, Suginome M. J. Am. Chem. Soc. 2010; 132: 2548
• 18a Lee JC. H, McDonald R, Hall DG. Nat. Chem. 2011; 3: 894
• 18b See also: Feng X, Jeon H, Yun J. Angew. Chem. Int. Ed. 2013; 52: 3989
• 19 Gaich T, Baran PS. J. Org. Chem. 2010; 75: 4657
• 20 For examples of the chemoselective cross-coupling of 1,1- and 1,2-diborylated olefinic species, see: Jiao J, Hyodo K, Hu H, Nakajima K, Nishihara Y. J. Org. Chem. 2014; 79: 285
• 21 Endo K, Ohkubo T, Hirokami M, Shibata T. J. Am. Chem. Soc. 2010; 132: 11033
• 22 Sun C, Potter B, Morken JP. J. Am. Chem. Soc. 2014; 136: 6534
• 23 Mlynarski SN, Schuster CH, Morken JP. Nature (London, U.K.) 2014; 505: 386
• 24 Fyfe JW. B, Seath CP, Watson AJ. B. Angew. Chem. Int. Ed. 2014; 53: 12077