Amino-Indanol-Catalyzed Asymmetric Michael Additions of Oxindoles to Protected 2-Amino-1-nitroethenes for the Synthesis of 3,3′-Disubstituted Oxindoles Bearing α,β-Diamino Functionality

• Published in: Journal of organic chemistry 2011-05, Vol.76 (10), p.4008-4017
• Main Authors: Liu, Xiong-Li, Wu, Zhi-Jun, Du, Xi-Lin, Zhang, Xiao-Mei, Yuan, Wei-Cheng
• Format: Article
• Language: English
• Subjects: Alicyclic compounds; Alicyclic compounds, terpenoids, prostaglandins, steroids; Amines - chemistry; Catalysis; Chemistry; Exact sciences and technology; Heterocyclic compounds; Heterocyclic compounds with only one n hetero atom and condensed derivatives; Indans - chemistry; Indoles - chemical synthesis; Indoles - chemistry; Nitro Compounds - chemistry; Organic chemistry; Preparations and properties
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo2004378

An organocatalytic asymmetric Michael addition reaction of 3-substituted oxindoles to protected 2-amino-1-nitroethenes has been developed. The reaction is catalyzed by a simple and readily available amino-indanol derivative and affords the desired products in very high yields (up to 99%) with excellent diastereoselectivities (up to >99:1) and very good enantioselectivities (up to 90%). Significantly, this study provides a general catalytic method for the construction of 3,3′-disubstituted oxindoles bearing α,β-diamino functionality as well as vicinal chiral quaternary/tertiary stereocenters. The potential utility of the protocol also had been demonstrated by gram-scale reaction and the versatile conversion of product. Furthermore, On the basis of the comprehensive experimental results and the absolute configuration of one of the Michael adducts, a work model was also proposed to explain the origin of asymmetric induction.