Copper-Catalyzed Oxidation of Deoxybenzoins to Benzils under Aerobic Conditions

Abstract

A novel copper-catalyzed approach to benzils from readily available deoxybenzoins under neutral conditions using air as the oxidant has been developed. The reaction tolerates a variety of useful substituents including chloro, bromo, iodo, keto, ester, and cyano groups.

Key words

copper - catalysis - oxidation - deoxybenzoins - benzils

• References

• 1a Battistuzzi G, Cacchi S, Fabrizi G. Eur. J. Org. Chem. 2002; 2671
• 1b Battistuzzi G, Cacchi S, Fabrizi G, Marinelli F, Parisi LM. Org. Lett. 2002; 4: 1355
• 1c Cacchi S, Fabrizi G. Chem. Rev. 2005; 105: 2873
• 1d Cacchi S, Fabrizi G, Goggiamani A. Curr. Org. Chem. 2006; 10: 1423
• 1e Cacchi S, Fabrizi G. Chem. Rev. 2011; 111: PR215
• 1f Cacchi S, Fabrizi G, Filisti E. Org. Lett. 2008; 10: 2629
• 1g Cacchi S, Fabrizi G, Goggiamani A, Sferrazza A. Synlett 2009; 1277
• 1h Bernini R, Cacchi S, Fabrizi G, Filisti E, Sferrazza A. Synlett 2009; 1245
• 1i Cacchi S, Fabrizi G, Goggiamani A, Perboni A, Sferrazza A, Stabile P. Org. Lett. 2010; 12: 3279
• 1j Bagnoli L, Cacchi S, Fabrizi G, Goggiamani A, Scarponi C, Tiecco M. J. Org. Chem. 2010; 75: 2134
• 1k Cacchi S, Fabrizi G, Goggiamani A. Org. Biomol. Chem. 2011; 9: 641
• 1l Cacchi S, Fabrizi G, Goggiamani A, Sferrazza A. Org. Biomol. Chem. 2011; 9: 1727
• 1m Cacchi S, Fabrizi G, Goggiamani A, Iazzetti A, Madec D, Poli G, Prestatt G. Org. Biomol. Chem. 2011; 9: 8233
• 2a Koike T, Murata K, Ikariya T. Org. Lett. 2000; 2: 3833
• 2b Deng X, Mani NS. Org. Lett. 2006; 8: 269
• 2c Samai S, Nandi GC, Singh P, Singh MS. Tetrahedron 2009; 65: 10155
• 2d Das PJ, Sarkar S. Chem. Biol. Interface 2011; 1: 95
• 2e Kumar D, Kommi DN, Bollineni N, Patel AR, Asit K, Chakraborti AK. Green Chem. 2012; 14: 2038
• 2f Ramesh K, Murthy SN, Karnakar K, Nageswar YV. D, Vijayalakhshmi K, Prabavathi Devi BL.A, Prasad RB. N. Tetrahedron Lett. 2012; 53: 1126
• 3a Corey EJ, Schaefer JP. J. Am. Chem. Soc. 1960; 82: 917
• 3b McKillop A, Swann BP, Ford ME, Taylor EC. J. Am. Chem. Soc. 1973; 95: 3641
• 3c Bauer DP, Macomber RS. J. Org. Chem. 1975; 40: 1990
• 3d Wasserman HH, Ives JL. J. Am. Chem. Soc. 1976; 98: 7868
• 3e De Kimpe N, Verhé R, De Buyck I, Schamp N. J. Org. Chem. 1978; 43: 2933
• 3f Wasserman HH, Ives JL. J. Org. Chem. 1985; 50: 3573
• 3g Rathore R, Saxena N, Chandrasekaran S. Synth. Commun. 1986; 16: 12
• 3h Bonadies F, Bonini C. Synth. Commun. 1986; 18: 1573
• 3i Jiang Q, Joshi BS, Pelletier SW. Tetrahedron Lett. 1991; 32: 5283
• 3j Lee JC, Park H, Park JY. Tetrahedron Lett. 2002; 43: 5661
• 3k Park BS, Lee HM, Cho S. Bull. Korean Chem. Soc. 2007; 28: 871
• 4 Qi C, Jiang H, Huang L, Chen Z, Chen H. Synthesis 2011; 387

For selected references, see:
• 5a Gamez P, Aubel PG, Driessen WL, Reedijk J. Chem. Soc. Rev. 2001; 30: 376
• 5b Geisslmeir D, Jary WG, Falk H. Monatsh. Chem. 2005; 136: 1591
• 5c Punniyamurthy T, Rout L. Coord. Chem. Rev. 2008; 252: 134
• 5d Conde A, Diaz-Requejo MM, Perez PJ. Chem. Commun. 2011; 47: 8154
• 5e Liu Q, Wu P, Yang Y, Zeng Z, Liu J, Yi H, Lei A. Angew. Chem. Int. Ed. 2012; 51: 4666
• 5f Ahmad JU, Raeisaenen MT, Leskelae M, Repo T. Appl. Catal., A 2012; 411-412: 180

For selected references on the oxidation of benzoins to benzils, see:
• 6a Macaione DP, Wentworth SE. Synthesis 1974; 716
• 6b Depreux P, Bethegnies G, Marcincal-Lefebvre A. J. Chem. Educ. 1988; 65: 553
• 6c Varma RS, Kumar D, Dahiya R. J. Chem. Res., Synop. 1998; 324
• 6d Tymonko SA, Nattier BA, Mohan RS. Tetrahedron Lett. 1999; 40: 7657
• 6e Sachdev D, Naik MA, Dubey A, Mishra BG. Catal. Commun. 2010; 11: 684
• 7 Fox JM, Huang X, Chieffi A, Buchwald SL. J. Am. Chem. Soc. 2000; 122: 1360
• 8 Bordwell FG, Knipe AC. J. Am. Chem. Soc. 1971; 93: 3416
• 9 Prakash O, Kumar R, Sharma D, Pannu K, Kamal R. Synlett 2007; 2189