Decarboxylative Claisen Condensations with Substituted Malonic Acid Half Oxyesters

Abstract

A decarboxylative Claisen condensation involving substituted malonic acid half oxyesters (SMAHOs) as pronucleophiles has been developed. The addition of their magnesium enolates to various acyl donors allows the synthesis of functionalized α-substituted β-keto esters in moderate to excellent yields (13–96%). In addition to acyl chlorides and acid anhydrides, these conditions proved efficient for the use of carboxylic acids as acylating agents, thus allowing to greatly extend the scope of this transformation (32 examples overall).

Key words

Claisen condensation - carboxylic acids - decarboxylation - acylation - dicarbonyl compounds

• References

• 1 Bernardi L, Fichi M, Franchini MC, Ricci A. Org. Biomol. Chem. 2012; 10: 2911
• 2 Gui J, Zhou Q, Pan C.-M, Yabe Y, Burns AC, Collins MR, Ornelas MA, Ishihara Y, Baran PS. J. Am. Chem. Soc. 2014; 136: 4853
• 3 Wang M, Zhao Y, Zhao Y, Shi Z. Sci. Adv. 2020; 6: eaba0946
• 4 Pan Y, Tan C.-H. Synthesis 2011; 2044
• 5 Wang Z.-L. Adv. Synth. Catal. 2013; 355: 2745
• 6 Heath RJ, Rock CO. Nat. Prod. Rep. 2002; 19: 581
• 7 Austin MB, Izumikawa M, Bowman ME, Udwary DW, Ferrer J.-L, Moore BS, Noel JP. J. Biol. Chem. 2004; 279: 45162
• 8 Xavier T, Condon S, Pichon C, Le Gall E, Presset M. Eur. J. Org. Chem. 2022; e202101392
• 9 Rodríguez N, Goossen LJ. Chem. Soc. Rev. 2011; 40: 5030
• 10 Liu P, Zhang G.-H, Sun P.-P. Org. Biomol. Chem. 2016; 14: 10763
• 11 Galat AA. J. Am. Chem. Soc. 1946; 68: 376
• 12 List B, Doehring A, Hechavarria Fonseca MT, Job A, Rios Torres R. Tetrahedron 2006; 476
• 13 Xavier T, Condon S, Pichon C, Le Gall E, Presset M. Org. Lett. 2019; 21: 6135
• 14 Ricci A, Pettersen D, Bernardi L, Fini F, Fochi M, Herrera RP, Sgarzani V. Adv. Synth. Catal. 2007; 349: 1037
• 15 Baudoux J, Lefebvre P, Legay R, Lasne M.-C, Rouden J. Green Chem. 2010; 12: 252
• 16 Xavier T, Condon S, Pichon C, Le Gall E, Presset M. J. Org. Chem. 2021; 86: 5452
• 17 Benetti S, Romagnoli R, De Risi C, Spalluto G, Zanirato V. Chem. Rev. 1995; 95: 1065
• 18 Ireland RE, Marshall JA. J. Am. Chem. Soc. 1959; 81: 2907
• 19 Clay RJ, Collom TA, Karrick GL, Wemple J. Synthesis 1993; 290
• 20 Schmidt U, Leitenberger V, Griesser H, Schmidt J, Meyer R. Synthesis 1992; 1248
• 21 Schmidt U, Griesser H, Lieberknecht A, Schmidt J, Grather T. Synthesis 1993; 765
• 22 Krysan DJ. Tetrahedron Lett. 1996; 37: 3303
• 23 Brooks DW, Lu LD.-L, Masamune S. Angew. Chem. Int. Ed. 1979; 18: 72
• 24 Misaki T, Nagase R, Matsumoto K, Tanabe Y. J. Am. Chem. Soc. 2005; 127: 2854
• 25 Xavier T, Condon S, Pichon C, Le Gall E, Presset M. Beilstein J. Org. Chem. 2021; 17: 2085
• 26 Blaquiere N, Shore DG, Rousseaux S, Fagnou K. J. Org. Chem. 2009; 74: 6190
• 27 Krapcho AP. ARKIVOC 2007; (ii): 1
• 28 Commercially available [CAS Reg. No.: 29540-54-3].
• 29 Zhang Z, Liu Y, Gong M, Zhao X, Zhang Y, Wang J. Angew. Chem. Int. Ed. 2010; 49: 1139
• 30 Guo S, Wang Q, Jiang Y, Yu J.-T. J. Org. Chem. 2014; 79: 11285
• 31 Josien H, Curran DP. Tetrahedron 1997; 53: 8881
• 32 Knobloch E, Brückner R. Synthesis 2008; 2229
• 33 Bagdasarian AL, Popov S, Wigman B, Wei W, Lee W, Nelson HM. Org. Lett. 2020; 22: 7775
• 34 Carini DJ, Duncia JV, Aldrich PE, Chiu AT, Johnson AL, Pierce ME, Price WA, Santella JB. III, Wells GJ, Wexler RR, Wong PC, Yoo S.-E, Timmermans PB. M. W. M. J. Med. Chem. 1991; 34: 2525
• 35 Basavaiah D, Muthukumaran K. Tetrahedron 1998; 54: 4943
• 36 Chong S, Su Y, Wu L, Zhang W, Ma J, Chen X, Huang D, Wang K.-H, Hu Y. Synthesis 2016; 48: 1359
• 37 Basavaiah D, Muthukumaran K. Synth. Commun. 1999; 29: 713
• 38 Asokan CV, Bhattacharji S, Ila H, Junjappa H. Synthesis 1988; 281