关键词: C–H activation cobalt deuterium hydrogen isotope exchange isotopic labeling α-diimine

来  源:   DOI:10.1021/acscatal.7b02051   PDF(Sci-hub)   PDF(Pubmed)

Abstract:
Cobalt dialkyl complexes bearing α-diimine ligands proved to be active precatalysts for the nondirected, C(sp3)-H selective hydrogen isotope exchange (HIE) of alkylarenes using D2 gas as the deuterium source. Alkylarenes with a variety of substitution patterns and heteroatom substituents on the arene ring were successfully labeled, enabling high levels of incorporation into primary, secondary, and tertiary benzylic C(sp3)-H bonds. In some cases, the HIE proceeded with high diastereoselectivity and application of the cobalt-catalyzed method to enantioenriched substrates with benzylic stereocenters provided enantioretentive hydrogen isotope exchange at tertiary carbons.
摘要:
带有α-二亚胺配体的钴二烷基配合物被证明是非定向,使用D2气体作为氘源的烷基芳烃的C(sp3)-H选择性氢同位素交换(HIE)。成功标记了芳烃环上具有多种取代模式和杂原子取代基的烷基芳烃,能够高水平地融入小学,次要,和叔苄基C(sp3)-H键。在某些情况下,HIE以高的非对映选择性进行,并将钴催化方法应用于具有苄基立体中心的富含对映体的底物,在叔碳上提供了对映体保留性氢同位素交换。
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