Diastereoselective synthesis of 2-methoxyimidoyl-oxiranes via dimethyl phosphite-mediated coupling of alpha-keto N-sulfinyl imidates with aldehydes
Diastereoselective synthesis of 2-methoxyimidoyl-oxiranes via dimethyl phosphite-mediated coupling of alpha-keto N-sulfinyl imidates with aldehydes
复制标题
通过亚磷酸二甲酯介导的α-酮N-亚磺酰亚胺酸酯与醛的偶联非对映选择性合成2-甲氧基亚氨基环氧乙烷
DOI：
10.1039/c6cc07723d
复制
发表时间：
2016
影响因子：
4.9
通讯作者：
Xu Yan-Jun
中科院分区：
文献类型：
--
作者：
Huang Wei;Liu Hui;Lu Chong-Dao;Xu Yan-Jun
报道了亚磷酸二甲酯引发的 α-酮基 N-叔丁基亚磺酰亚胺酯与醛的偶联。环氧化物的形成涉及级联转化，该级联转化由碱促进的亚磷酸酯加成至α-酮亚胺酯引发，随后进行[1,2]-磷酸-布鲁克重排。这会生成 α-膦酰氧基烯醇化物，随后被醛拦截，导致 [1,4] O→O 二烷氧基膦酰基迁移，最终导致分子内闭环。该方案用于以中等到高产率合成一系列对映体富集的反式-α,β-环氧亚氨酸酯，并具有优异的非对映选择性。
Dimethyl phosphite-initiated coupling of α-keto N-tert-butylsulfinyl imidates with aldehydes is reported. The epoxide formation involves a cascade transformation initiated by base-promoted addition of phosphite to α-ketoimidates, followed by [1,2]-phospha-Brook rearrangement. This generates α-phosphonyloxy enolates that are subsequently intercepted by aldehydes, leading to [1,4] O→O dialkoxyphosphinyl migration and finally to intramolecular ring closure. This protocol was used to synthesize a range of enantioenriched trans-α,β-epoxy imidates in moderate to high yields with excellent diastereoselectivities.