Highly Enantioselective Michael Addition of Dithiomalonates to Nitroolefins Catalyzed by New Bifunctional Chiral Thioureas

Jia-Ni Yuan and Hui-Xia Liu contributed equally.

Abstract

We report a highly efficient asymmetric Michael addition of dithiomalonates to trans-β-nitroolefins catalyzed by versatile cinchona-based bifunctional thioureas, which provides the corresponding adducts in high yields (up to 92%) and with excellent enantioselectivities (up to 99% ee) under mild conditions. Replacement of the catalyst with its pseudo-enantiomer gives the Michael adducts with opposite configuration in similar yields and enantioselectivities.

Key words

Michael addition - cinchona alkaloids - chirality - hydrogen bonds - γ-aminobutyric acids

• References

• 1a List B. Chem. Rev. 2007; 107: 5413
• 1b Gaunt MJ. Johansson CC. McNally A. Vo NT. Drug Discovery Today 2007; 12: 8
• 1c Gratzer K. Gururaja GN. Waser M. Eur. J. Org. Chem. 2013; 4471
• 1d Bertelsen SR. Jørgensen KA. Chem. Soc. Rev. 2009; 38: 2178
• 1e Lifchits O. Mahlau M. Reisinger CM. Lee A. Farés C. Polyak I. Gopakumar G. Thiel W. List B. J. Am. Chem. Soc. 2013; 135: 6677
• 1f Thirupathi B. Breitler S. Reddy KM. Corey EJ. J. Am. Chem. Soc. 2016; 138: 10842
• 1g Brown AR. Kuo W. Jacobsen EN. J. Am. Chem. Soc. 2010; 132: 9286
• 1h Yeung CS. Ziegler RE. Porco JA. Jacobsen EN. J. Am. Chem. Soc. 2014; 136: 13614
• 2a Shi X. He W. Li H. Zhang X. Zhang SY. Tetrahedron Lett. 2011; 52: 3204
• 2b Li H. Zhang X. Shi X. Ji N. He W. Zhang SY. Zhang BL. Adv. Synth. Catal. 2012; 354: 2264
• 2c Liu YL. Wang X. Wang XY. He W. Org. Biomol. Chem. 2014; 12: 3163
• 2d Ji N. Yuan JN. Xue SS. Zhang JN. He W. Tetrahedron 2016; 72: 512
• 3 Monaco MR. Prévost S. List B. J. Am. Chem. Soc. 2014; 136: 16982
• 4 Okino T. Hoashi Y. Takemoto Y. J. Am. Chem. Soc. 2003; 125: 12672
• 5a Guo HM. Li JG. Qu GR. Zhang XM. Yuan WC. Chirality 2011; 23: 514
• 5b Cao CL. Ye M.-C. Sun XL. Tang Y. Org. Lett. 2006; 8: 2901
• 5c Okino T. Hoashi Y. Furukawa T. Xu X. Takemoto Y. J. Am. Chem. Soc. 2005; 127: 119
• 5d Inokuma T. Hoashi Y. Takemoto Y. J. Am. Chem. Soc. 2006; 128: 9413
• 5e Liao YH. Chen WB. Wu ZJ. Du XL. Cun LF. Zhang XM. Yuan WC. Adv. Synth. Catal. 2010; 352: 827
• 6a Ye WP. Jiang ZY. Zhao YJ. Goh SL. M. Leow D. Soh YT. Tan CH. Adv. Synth. Catal. 2007; 349: 2454
• 6b Jiang ZY. Yang YY. Pan YH. Zhao YJ. Liu HJ. Tan CH. Chem. Eur. J. 2009; 15: 4925
• 6c Hatano M. Moriyama K. Maki T. Ishihara K. Angew. Chem. Int. Ed. 2010; 49: 3823
• 7a Bae HY. Some S. Lee JH. Kim J. Song MJ. Lee S. Zhang YJ. Song CE. Adv. Synth. Catal. 2011; 353: 3196
• 7b Massolo E. Benaglia M. Genoni A. Annunziata R. Celentano G. Gaggero N. Org. Biomol. Chem. 2015; 13: 5591
• 7c Lubkoll J. Wennemers H. Angew. Chem. Int. Ed. 2007; 46: 6841
• 7d Ricci A. Pettersen D. Bernardi L. Fini F. Fochi M. Herrera RP. Sgarzani V. Adv. Synth. Catal. 2007; 349: 1037
• 7e Bae HY. Song CE. ACS Catal. 2015; 5: 3613
• 7f Ordóñez M. Cativiela C. Estudillo IN. R. Tetrahedron: Asymmetry 2016; 27: 999
• 8a Tokuyama H. Yokoshima S. Yamashita T. Fukuyama T. Tetrahedron Lett. 1998; 39: 3189
• 8b Miyazaki T. Hanya Y. Tokuyama H. Fukuyama T. Synlett 2004; 477
• 8c Mori Y. Seki M. Adv. Synth. Catal. 2007; 349: 2027
• 8d Cherney AH. Reisman SE. Tetrahedron 2014; 70: 3259
• 9 Jin H. Kim ST. Hwang G. Ryu DH. J. Org. Chem. 2016; 81: 3263
• 10 Sim JH. Song CE. Angew. Chem. Int. Ed. 2017; 56: 1835
• 11a Dambrova M. Zvejniece L. Liepinsh E. Cirule H. Zharkova O. Veinberg G. Kalvinsh I. Eur. J. Pharmacol. 2008; 538: 128
• 11b Liu HX. Yuan JN. Tian QQ. Ji N. He W. J. Mater. Sci. Chem. Eng. 2017; 5: 25
• 12 Wang B. Liu YX. Sun C. Wei ZL. Cao JG. Liang DP. Lin YJ. Duan HF. Org. Lett. 2014; 16: 6432