We herein describe a Ni-catalyzed formal hydroamidation of readily available α,β-unsaturated carbonyl compounds to afford valuable chiral β-amino acid derivatives (up to >99:1 e.r.) using dioxazolones as a robust amino source. A wide range of alkyl-substituted olefins conjugated to esters, amides, thioesters, and ketones were successfully amidated at the β-position with excellent enantioselectivity for the first time. Combined experimental and computational mechanistic studies supported our working hypothesis that this unconventional β-amidation of unsaturated carbonyl substrates can be attributed to the polar-matched migratory olefin insertion of an (amido)(Cl)Ni^II intermediate, in situ generated from the dioxazolone precursor.

中文翻译：

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通过镍催化的甲醛缩甲醛对映选择性获得 β-氨基羰基


我们在此描述了容易获得的α,β-不饱和羰基化合物的Ni催化形式加氢酰胺化，以使用二恶唑酮作为强大的氨基源提供有价值的手性β-氨基酸衍生物（高达>99:1 e.r.）。首次成功地将多种烷基取代烯烃与酯、酰胺、硫酯和酮共轭在 β 位进行酰胺化，并具有优异的对映选择性。实验和计算机制相结合的研究支持了我们的工作假设，即不饱和羰基底物的这种非常规 β-酰胺化可归因于 (amido)(Cl)Ni ^II 中间体的极性匹配迁移烯烃插入，由二恶唑酮前体原位生成。