Asymmetric synthesis of α,β-diamino acid derivatives with an aziridine-, azetidine- and γ-lactone-skeleton via Mannich-type additions across α-chloro-N-sulfinylimines
Asymmetric synthesis of α,β-diamino acid derivatives with an aziridine-, azetidine- and γ-lactone-skeleton via Mannich-type additions across α-chloro-N-sulfinylimines
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DOI：
10.1039/c2ob06637h
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发表时间：
2012-01-01
影响因子：
3.2
通讯作者：
De Kimpe, Norbert
中科院分区：
文献类型：
--
作者：
Callebaut, Gert;Mangelinckx, Sven;De Kimpe, Norbert
通过N-(二苯亚甲基)甘氨酸酯在手性α-氯-N-对甲苯磺胺上的高非对映选择性Mannich反应，高效地合成了新的手性伽马-氯-α，β-二氨基酸衍生物。用于甘氨酸烯醇酸盐形成的碱LDA或LiHMDS的影响对于Mannich反应的反/合成非对映选择性是非常重要的。事实证明，伽马-氯-α，β-二氨基酸衍生物是向光学纯的反式和合成-β，伽马-氮杂环-α-氨基酸酯以及随后的环转化为反式-3-氨基氮杂环丁烷-2-羧酸衍生物和α，β-二氨基-伽马丁内酯的极好的构造物。
The efficient asymmetric synthesis of new chiral gamma-chloro-alpha,beta-diamino acid derivatives via highly diastereoselective Mannich-type reactions of N-(diphenylmethylene) glycine esters across a chiral alpha-chloro-N-p-toluenesulfinylimine was developed. The influence of the base, LDA or LiHMDS, used for the formation of the glycine enolates, was of great importance for the anti-/syn-diastereoselectivity of the Mannich-type reaction. The gamma-chloro-alpha,beta-diamino acid derivatives proved to be excellent building blocks for ring closure towards optically pure anti-and syn-beta,gamma-aziridino-alpha-amino esters, and subsequent ring transformation into trans-3-aminoazetidine-2-carboxylic acid derivatives and alpha,beta-diamino-gamma-butyrolactones.