Stereodivergent Synthesis of Carbocyclic Quaternary α‐Amino Acid Derivatives Containing Two Contiguous Stereocenters
Stereodivergent Synthesis of Carbocyclic Quaternary
α‐Amino
Acid Derivatives Containing Two Contiguous Stereocenters
复制标题
含两个连续立构中心的碳环季铵α-氨基酸衍生物的立构发散合成
DOI：
10.1002/cjoc.202100824
复制
发表时间：
2022
影响因子：
5.4
通讯作者：
Chun‐Jiang Wang
中科院分区：
文献类型：
--
作者：
Cong Fu;Qi Xiong;L. Xiao;Ling He;Tian Bai;Zongpeng Zhang;Xiuqin Dong;Chun‐Jiang Wang
综合总结通过连续双Cu/Ir催化的不对称烯丙基化和闭环复分解，提出了一种立体发散合成具有两个连续立构中心的碳环α-季铵氨基酸衍生物的新方法。各种五元和六元碳环α-季铵氨基酸衍生物可以很容易地以良好到高的产率获得，并且具有独特的区域选择性、优异的非对映选择性（13:1- > 20:1 dr）和对映选择性（通常> 99% ee）。特别值得注意的是，当前的协议也是一种多功能合成工具，用于具有挑战性的七元和八元碳环 α-氨基酸衍生物的立体发散结构。这些重要分子的所有四种立体异构体都可以通过手性 Cu/Ir 催化体系的排列来精确合成。该策略的威力已被证明可以轻松获得一些具有生物活性的手性分子，例如螺乙内酰脲。
Comprehensive SummaryA novel approach to stereodivergent synthesis of carbocyclic α‐quaternary amino acid derivatives, bearing two contiguous stereocenters, is proposed through sequential dual Cu/Ir‐catalyzed asymmetric allylation and ring‐closing metathesis. A variety of five and six‐membered carbocyclic α‐quaternary amino acid derivatives could be readily achieved in good to high yields with exclusive regioselectivities, excellent diastereoselectivities (13: 1‐ > 20:1 dr) and enantioselectivities (generally >99% ee). Of particular note is that the current protocol is also a versatile synthetic tool for the stereodivergent construction of the challenging seven and eight‐membered carbocyclic α‐amino acid derivatives. All four stereoisomers of these important molecules could be precisely synthesized through the permutation of chiral Cu/Ir catalytic system. The power of this strategy has been demonstrated for the facile access to some biologically active chiral molecules, such as spiro‐hydantoins.