Copper-Mediated Oxidative α-Arylation of Carbonyl Compounds with Boronic Acid Derivatives

Abstract

We have developed copper-promoted oxidative carbon–­carbon bond-forming reactions to synthesize α-aryl carbonyl compounds. The use of weak C–H acids as nucleophiles under Chan–Evans–Lam-type conditions enables α-arylation reactivity complementary to that of established copper- or palladium-catalyzed cross-coupling methodologies that employ aryl (pseudo)halides. This Synpacts article will discuss key observations and experimental parameters that allowed for reaction development, substrate scope studies, and applications in bioactive molecule synthesis and functionalization.

1 Introduction

2 Oxidative Cross-Coupling of Activated Methylenes and Organo­boron Reagents

3 Decarboxylative Oxidative Arylation of Malonic Acid Derivatives

4 Conclusion

Key words

aerobic catalysis - arylation - boron - copper - cross-coupling

• References

• 1a Liu C, Zhang H, Shi W, Lei AW. Chem. Rev. 2011; 111: 1780
• 1b Liu C, Liu D, Lei AW. Acc. Chem. Res. 2014; 47: 3459
• 1c Guo FH, Clift MD, Thomson RJ. Eur. J. Org. Chem. 2012; 4881
• 2a Chan DM. T, Monaco KL, Wang RP, Winters MP. Tetrahedron Lett. 1998; 39: 2933
• 2b Evans DA, Katz JL, West TR. Tetrahedron Lett. 1998; 39: 2937
• 2c Lam PY. S, Clark CG, Saubern S, Adams J, Winters MP, Chan DM. T, Combs A. Tetrahedron Lett. 1998; 39: 2941
• 2d Qiao JX, Lam PY. S. Recent Advances in Chan–Lam Coupling Reaction: Copper-­Promoted C–Heteroatom Bond Cross-Coupling Reactions with Boronic Acids and Derivatives. In Boronic Acids. Wiley-VCH; Weinheim: 2011: 315
• 3a Beletskaya IP, Cheprakov AV. Organometallics 2012; 31: 7753
• 3b Lam PY. S. Chan–Lam Coupling Reaction: Copper-­Promoted C-Element Bond Oxidative Coupling Reaction with Boronic Acids. In Synthetic Methods in Drug Discovery. Vol. 1. Blakemore DC, Doyle PM, Fobian YM. Chap. 7 The Royal Society of Chemistry; Cambridge: 2015: 242
• 4 Jiang Y, Ma D. Copper-Catalyzed Ligand-Promoted Ullmann-Type Coupling Reactions. In Catalysis without Precious Metals. Wiley-VCH; Weinheim: 2010: 213
• 5 Bunescu A, Wang Q, Zhu JP. Synthesis 2012; 44: 3811
• 6 Stevens JM, MacMillan DW. C. J. Am. Chem. Soc. 2013; 135: 11756
• 7 Moon PJ, Halperin HM, Lundgren RJ. Angew. Chem. Int. Ed. 2016; 55: 1894
• 8 Hall DG. Structure, Properties, and Preparation of Boronic Acid Derivatives. In Boronic Acids. Vol. 1. Hall DG. Wiley-VCH; Weinheim: 2011: 1
• 9a King AE, Brunold TC, Stahl SS. J. Am. Chem. Soc. 2009; 131: 5044
• 9b King AE, Ryland BL, Brunold TC, Stahl SS. Organometallics 2012; 31: 7948
• 10a Dejongh HA. P, Dejonge CR. H, Mijs WJ, Huysmans WG, Sinnige HJ. M, Klein WJ. D. J. Org. Chem. 1972; 37: 1960
• 10b Watanabe T, Ishikawa T. Tetrahedron Lett. 1999; 40: 7795
• 11 Minami T, Isonaka T, Okada Y, Ichikawa J. J. Org. Chem. 1993; 58: 7009
• 12 Guo C. Tetrahedron Lett. 2010; 51: 548
• 13 Cristau HJ, Cellier PP, Spindler JF, Taillefer M. Chem. Eur. J. 2004; 10: 5607
• 14 Pivsa-Art S, Fukui Y, Miura M, Nomura M. Bull. Chem. Soc. Jpn. 1996; 69: 2039
• 15 Tromp M, van Strijdonck GP. F, van Berkel SS, van den Hoogenband A, Feiters MC, de Bruin B, Fiddy SG, van der Eerden AM. J, van Bokhoven JA, van Leeuwen P, Koningsberger DC. Organometallics 2010; 29: 3085
• 16 Moon PJ, Yin S, Lundgren RJ. J. Am. Chem. Soc. 2016; 138: 13826
• 17a Staunton J, Weissman KJ. Nat. Prod. Rep. 2001; 18: 380
• 17b Smith S, Tsai SC. Nat. Prod. Rep. 2007; 24: 1041
• 18a Fortner KC, Shair MD. J. Am. Chem. Soc. 2007; 129: 1032
• 18b Lalic G, Aloise AD, Shair MD. J. Am. Chem. Soc. 2003; 125: 2852
• 18c Magdziak D, Lalic G, Lee HM, Fortner KC, Aloise AD, Shair MD. J. Am. Chem. Soc. 2005; 127: 7284
• 19a Shang R, Ji DS, Chu L, Fu Y, Liu L. Angew. Chem. Int. Ed. 2011; 50: 4470
• 19b Feng YS, Wu W, Xu ZQ, Li Y, Li M, Xu HJ. Tetrahedron 2012; 68: 2113
• 20 Johansson CC. C, Colacot TJ. Angew. Chem. Int. Ed. 2010; 49: 676
• 21 Siesel D. WO 2010138484, 2010