Unexpected Iodine-Promoted Aerobic Oxidation of α-Cyano-δ-keto Esters: A Facile Synthesis of α,δ-Dicarbonyl Esters

Abstract

An efficient and green method for the synthesis of various α,δ-dicarbonyl esters has been developed via a conjugate addition of ethyl cyanoacetates to chalcones and subsequent iodine-promoted aerobic oxidation. The present protocol features mild reaction conditions, high efficiency, easily available starting materials, and broad substrate scope.

Key words

cyanoacetates - α,δ-dicarbonyl esters - molecular iodine - aerobic oxidation - two-step synthesis

• References

• 1a Geraghty NW. A, Morris NM. Synthesis 1989; 603
• 1b Paterson I, Xuan M, Dalby SM. Angew. Chem. Int. Ed. 2014; 53: 7286
• 2a Ferreira VF, de Souza MC. B. V, Cunha AC, Pereira LO. R, Ferreira ML. G. Org. Prep. Proced. Int. 2001; 33: 411
• 2b Fuchs PJ. W, Zeitler K. J. Org. Chem. 2017; 82: 7796
• 3a Rao HS. P, Jothilingam SJ. J. Org. Chem. 2003; 68: 5392
• 3b Khaghaninejad S, Heravi MM. Adv. Heterocycl. Chem. 2014; 111: 95
• 4 Chan C.-K, Chan Y.-L, Tsai Y.-L, Chang M.-Y. J. Org. Chem. 2016; 81: 8112
• 5 Mortensen DS, Rodríguez AL, Carlson KE, Sun J, Katzenellenbogen BS, Katzenellenbogen AJ. J. Med. Chem. 2001; 44: 3838
• 6a Zhang J, Xing C, Tiwari B, Chi YR. J. Am. Chem. Soc. 2013; 135: 8113
• 6b Wilde MM. D, Gravel M. Angew. Chem. Int. Ed. 2013; 52: 12651
• 6c Yang KS, Nibbs AE, Türkmen YE, Rawal VH. J. Am. Chem. Soc. 2013; 135: 16050
• 6d Yetra SR, Patra A, Biju AT. Synthesis 2015; 47: 1357
• 7a Xue S, Li L.-Z, Liu Y.-K, Guo Q.-X. J. Org. Chem. 2006; 71: 215
• 7b Voituriez A, Zimmer LE, Charette AB. J. Org. Chem. 2010; 75: 1244
• 8a Yasuda M, Tsuji S, Shigeyoshi Y, Baba A. J. Am. Chem. Soc. 2002; 124: 7440
• 8b Liu C, Deng Y, Wang J, Yang Y, Tang S, Lei A. Angew. Chem. Int. Ed. 2011; 50: 7337
• 9a Avetta CT. Jr, Konkol LC, Taylor CN, Dugan KC, Stern CL, Thomson RJ. Org. Lett. 2008; 10: 5621
• 9b Clift MD, Thomson RJ. J. Am. Chem. Soc. 2009; 131: 14579
• 9c Xie J, Huang Z.-Z. Chem. Commun. 2010; 46: 1947
• 9d Casey BM, Flowers RA. J. Am. Chem. Soc. 2011; 133: 11492
• 10 Kim SH, Kim KH, Kim JN. Adv. Synth. Catal. 2011; 353: 3335

For selected reviews, see:
• 11a French AN, Bissmire S, Wirth T. Chem. Soc. Rev. 2004; 33: 354
• 11b Togo H, Iida S. Synlett 2006; 2159

For selected examples, see:
• 12a Guo Y, Wang G, Wei L, Wan J.-P. J. Org. Chem. 2019; 84: 2984
• 12b Geng X, Wang C, Zhao P, Zhou Y, Wu Y.-D, Wu A.-X. Org. Lett. 2019; 21: 4939
• 12c Geng X, Wang C, Huang C, Zhao P, Zhou Y, Wu Y.-D, Wu A.-X. Org. Lett. 2019; 21: 7504
• 12d Ni B, He Y, Rong X, Niu T. Synlett 2019; 30: 1830
• 12e Gataullin RR, Mescheryakova ES, Sultanov RM, Fatykhov AA, Khalilov LM. Synthesis 2019; 51: 3485
• 13a Xu H, Li Y, Xing M, Jia J, Han L, Ye Q, Gao J. Chem. Lett. 2015; 44: 574
• 13b Xu H, Wang F.-J, Xin M, Zhang Z. Eur. J. Org. Chem. 2016; 925
• 13c Xu H, Liu H.-W, Chen K, Wang G.-W. J. Org. Chem. 2018; 83: 6035
• 14a Li Y, Xu H, Xing M, Huang F, Jia J, Gao J. Org. Lett. 2015; 17: 3690
• 14b Xu H, Liu H.-W, Lin H.-S, Wang G.-W. Chem. Commun. 2017; 53: 12477
• 15 Xu H, Zeng J.-C, Wang F.-J, Zhang Z. Synthesis 2017; 49: 1879
• 16 Xu H, Chen K, Liu H.-W, Wang G.-W. Org. Chem. Front. 2018; 5: 2864
• 17 Miao C.-B, Zhang M, Tian Z.-Y, Xi H.-T, Sun X.-Q, Yang H.-T. J. Org. Chem. 2011; 76: 9809