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研究了醋酸铑[Rh2(OAc)4]、手性亚磺酰胺基脲和非手性磺酸共催化的α-重氮酯与酰胺化合物的不对称N—H插入反应.研究发现α-重氮酯在醋酸铑催化下形成金属卡宾,该金属卡宾与酰胺反应生成潜手性活泼叶立德中间体.在催化剂量的手性亚磺酰胺基脲和非手性磺酸存在下,潜手性叶立德中间体发生不对称质子化,合成了手性α-氨基酸衍生物.反应过程中,手性亚磺酰胺基脲和非手性磺酸作为“手性质子梭”催化不对称质子迁移从而实现了反应的对映选择性控制.该方法发展了非手性铑、手性亚磺酰胺基脲和非手性磺酸不对称共催化体系,为合成α-氨基酸衍生物提供了一种新途径,反应收率最高可达84%,对映选择性最高可达77%.
The asymmetric N-H insertion reaction of rhodium acetate [Rh2 (OAc) 4], chiral sulfinamide urea and achiral sulfonic acid catalyzed α-diazo ester with amide compounds was studied. It was found that α- Nitrogen ester catalyzed by rhodium acetate to form a metal carbene, the metal carbene reacted with amide to form a latent intramolecular active Ye Lide intermediates in the presence of a catalytic amount of chiral sulfinamide urea and achiral sulfonic acid, Asymmetric protonation of the intermediate results in the synthesis of chiral α-amino acid derivatives. During the reaction, chiral sulfinamide groups and achiral sulfonic acids catalyze the asymmetric proton transfer as a “chiral proton” The enantioselective control of the reaction was achieved.The asymmetric co-catalysis system of achiral rhodium, chiral sulfinamide and achiral sulfonic acid was developed, which provided a new method for the synthesis of α-amino acid derivatives Route, the reaction yield up to 84%, enantioselectivity up to 77%.