直接将伯醇转化为 1,2-氨基醇：通过氢自动转移实现邻苯二甲酰亚胺烯丙基的对映选择性铱催化羰基还原偶联。
Direct Conversion of Primary Alcohols to 1,2-Amino Alcohols: Enantioselective Iridium-Catalyzed Carbonyl Reductive Coupling of Phthalimido-Allene via Hydrogen Auto-Transfer.
机构信息
Department of Chemistry , University of Texas at Austin , Austin , Texas 78712 , United States.
出版信息
J Am Chem Soc. 2019 Sep 11;141(36):14136-14141. doi: 10.1021/jacs.9b08715. Epub 2019 Aug 29.
Abstract
The first catalytic enantioselective carbonyl (α-amino)allylations are described. Phthalimido-allene and primary alcohols -, - engage in hydrogen auto-transfer-mediated carbonyl reductive coupling by way of (α-amino)allyliridium-aldehyde pairs to form vicinal amino alcohols -, - with high levels of regio-, -diastereo-, and enantioselectivity. Reaction progress kinetic analysis and isotopic labeling studies corroborate a catalytic cycle involving turnover-limiting alcohol dehydrogenation followed by rapid allene hydrometalation.
摘要
首次描述了手性催化的羰基（α-氨基）烯丙基化反应。邻苯二甲酰亚胺基烯丙基化合物与伯醇在氢自动转移介导的羰基还原偶联反应中，通过（α-氨基）烯丙基铱-醛对形成高区域选择性、高非对映选择性和高对映选择性的偕氨基醇产物。反应进度动力学分析和同位素标记研究证实了一个涉及醇脱氢反应的催化循环，该反应是速控步骤，随后是快速的烯丙基氢金属化反应。
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