Lan Yun, Wang Chuan
Hefei National Laboratory for Physical Science at the Microscale, Department of Chemistry, Center for Excellence in Molecular Synthesis, University of Science and Technology of China, Hefei, Anhui, 230026, People's Republic of China.
Commun Chem. 2020 Apr 3;3(1):45. doi: 10.1038/s42004-020-0292-3.
Recently, transition-metal-catalyzed asymmetric dicarbofunctionalization of tethered alkenes has emerged as a powerful method for construction of chiral cyclic carbo- and heterocycles. However, all these reactions rely on facially selective arylmetalation of the pendant olefinic unit. Here, we successfully apply acylnickelation as the enantiodetermining step in the asymmetric nickel-catalyzed reductive carbo-acylation of aryl carbamic chloride-tethered alkenes with primary and secondary alkyl iodides as well as benzyl chlorides as the coupling partners, using manganese as a reducing agent. By circumventing the use of pre-generated organometallics, this reductive strategy enables the synthesis of diverse enantioenriched oxindoles bearing a quaternary stereogenic center under mild reaction conditions with high tolerance of a broad range of functional moieties.
最近，过渡金属催化的链烯基不对称双碳官能化反应已成为构建手性环状碳环和杂环的有力方法。然而，所有这些反应都依赖于侧链烯烃单元的面选择性芳基金属化反应。在此，我们成功地将酰基镍化反应作为对映体决定步骤，用于在不对称镍催化下，以锰作为还原剂，将芳基氨基甲酰氯连接的烯烃与伯、仲烷基碘以及苄基氯作为偶联伙伴进行还原碳酰化反应。通过避免使用预先生成的有机金属化合物，这种还原策略能够在温和的反应条件下，以高耐受性容纳广泛的官能团，合成多种带有季碳立体中心的对映体富集的氧化吲哚。
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