Ni-Catalyzed Regiodivergent and Stereoselective Hydroalkylation of Acyclic Branched Dienes with Unstabilized C(sp3) Nucleophiles,Journal of the American Chemical Society

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Ni-Catalyzed Regiodivergent and Stereoselective Hydroalkylation of Acyclic Branched Dienes with Unstabilized C(sp3) Nucleophiles
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2020-09-01 , DOI: 10.1021/jacs.0c08319
Wen Shao ₁ , Céline Besnard ₂ , Laure Guénée ₂ , Clément Mazet ₁

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Two complementary regiodivergent [(P,N)Ni]-catalyzed hydroalkylations of branched dienes are reported. When amides are employed as unstabilized C(sp3) nucleophiles, a highly regioselective 1,4-addition process is favored. The addition products are obtained in high yield and with excellent stereocontrol of the internal olefin. Using a chiral ligand and imides as carbon nucleophiles, a 3,4-addition protocol was developed enabling to construct two contiguous tertiary stereocenters in a single step with moderate to high levels of diastereocontrol and excellent enantiocontrol. Both methods operate under mild reaction conditions, display broad scope and excellent functional group tolerance. The synthetic potential of the 3,4-hydroalkylation reaction was established via a series of post-catalytic modifications.

中文翻译：

镍催化区域发散和立体选择性加氢烷基化无环支化二烯与不稳定的 C(sp3) 亲核试剂

报道了两种互补的区域发散 [(P,N)Ni] 催化的支化二烯加氢烷基化反应。当酰胺用作不稳定的 C(sp3) 亲核试剂时，高度区域选择性的 1,4-加成过程是有利的。以高收率获得加成产物，并且内烯烃具有优异的立体控制。使用手性配体和酰亚胺作为碳亲核试剂，开发了 3,4-加成方案，能够在一个步骤中构建两个连续的三级立体中心，具有中到高水平的非对映控制和出色的对映控制。这两种方法都在温和的反应条件下操作，表现出广泛的范围和优异的官能团耐受性。3,4-加氢烷基化反应的合成潜力是通过一系列后催化修饰建立的。

更新日期：2020-09-01

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