Nickel-Catalyzed 1,2-Carboamination of Alkenyl Alcohols
Nickel-Catalyzed 1,2-Carboamination of Alkenyl Alcohols
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DOI：
10.1021/jacs.1c07112
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发表时间：
2021-08-20
影响因子：
15
通讯作者：
Engle, Keary M.
中科院分区：
文献类型：
--
作者：
Kang, Taeho;Kim, Nana;Engle, Keary M.
报道了一种镍催化的未活化烯烃与芳基/烯基硼酸酯和亲电胺化试剂的醇导向的三组分顶空碳胺化反应。这种转化是通过专门定制的O-（2，6-二甲氧基苯甲酰基）羟胺亲电试剂实现的，所述亲电试剂抑制竞争性过程，包括醇底物和亲电试剂之间的不期望的β-氢化物消除和酯交换。该反应提供了所需的1，2-氨基甲酸酯的产品，通常具有高的区域和顺式非对映选择性，并表现出广泛的偶联伙伴和烯烃，包括复杂的天然产物。通过X射线晶体学分析证实，用环烯烃底物的立体化学结果的各种机械实验和分析支持有机镍（I）物种的醇定向svn插入。
An alcohol-directed, nickel-catalyzed three-component umpolung carboamination of unactivated alkenes with aryl/alkenylboronic esters and electrophilic aminating reagents is reported. This transformation is enabled by specifically tailored O-(2,6-dimethoxybenzoyOhydroxylamine electrophiles that suppress competitive processes, including undesired beta-hydride elimination and transesterification between the alcohol substrate and electrophile. The reaction delivers the desired 1,2-carboaminated products with generally high regio- and syn-diastereoselectivity and exhibits a broad scope of coupling partners and alkenes, including complex natural products. Various mechanistic experiments and analysis of the stereochemical outcome with a cyclic alkene substrate, as confirmed by X-ray crystallographic analysis, support alcohol-directed svn-insertion of an organonickel(I) species.