Precatalyst-Enabled Selectivity: Enantioselective NiH-catalyzed anti-Hydrometalative Cyclization of Alkynones to Endo- and Hetero-cyclic Allylic Alcohols
Precatalyst-Enabled Selectivity: Enantioselective NiH-catalyzed anti-Hydrometalative Cyclization of Alkynones to Endo- and Hetero-cyclic Allylic Alcohols
复制标题
预催化剂实现的选择性：对映选择性 NiH 催化的炔酮抗氢金属化环化为内环和杂环烯丙醇
DOI：
10.1002/anie.202110815
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发表时间：
2021
期刊：
影响因子：
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通讯作者：
Wen-Bo Liu
中科院分区：
文献类型：
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作者：
Xiao-Wen Zhang;Ming-Hui Zhu;Hai-Xiang Zeng;Qi-Yang Li;Wen-Bo Liu
本文报道了一种高对映选择性的NiH催化的炔酮氢环化反应，该反应具有不平行的反环和内环选择性。预催化剂的选择对调节区域选择性和对映选择性有重要影响。以Ni（OTs）_2/Phox为预催化剂，（EtO）_2MeSiH为氢化物源，以80：20-99：1的产率得到了一系列对映体富集的含O-、N-和S-杂环叔烯丙醇，产率为24- 81%。并进行了机理研究和综合应用。这项研究代表了一组烯丙醇的有效途径，这些烯丙醇无法通过最先进的偶联反应获得。
A highly enantioselective NiH‐catalyzed hydrocyclization of alkynones with unparalleledanti‐ and endocyclic selectivities is described. The choice of the precatalysts has significant influence in tuning the regio‐ and enantioselectivity. Using Ni(OTs)2/Phox as a precatalyst and (EtO)2MeSiH as a hydride source, an array of enantioenriched O‐, N‐, and S‐containing heterocyclic tertiary allylic alcohols are obtained in 24–81 % yields with 80:20–99:1 er. Mechanistic investigations and synthetic application are also carried out. This study represents an efficient access to a set of allylic alcohols that are unable to access by the state‐of‐the‐art coupling reactions.