氢胺化
区域选择性
烯烃
催化作用
酰胺
化学
组合化学
氢化物
产量(工程)
铑
有机化学
金属
材料科学
冶金
作者
Noah Wagner-Carlberg,Tomislav Rovis
标识
DOI:10.1021/acscatal.3c05075
摘要
Hydroamination of terminal alkenes represents a powerful and well-established way to introduce nitrogenous functionality to feedstock chemicals. Remote hydroamination reactions are far less known and represent a way to functionalize unactivated C(sp3) centers distal to the site of the alkene. These transformations commonly take place via metal-hydride-mediated chain walking, and as such, regioselectivity can be challenging. The remote introduction of amides is of particular interest due to their prevalence in pharmaceuticals. Herein we report a Rh(III)-catalyzed hydroamidation procedure to functionalize the terminal position of internal alkenes, using dioxazolones as amidation reagents and i-PrOH as a hydride source. The reaction proceeds with high yield and regioselectivity and tolerates a variety of functionality. Regioconvergent synthesis of a single linear amide from a mixture of isomeric alkenes is demonstrated. Key to the development of this reaction was determining that inorganic bases poison the catalyst and identifying a suitable trialkylamine replacement.
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