4.8 Article

Rh(I)-Catalyzed Hydroamidation of Olefins via Selective Activation of N-H Bonds in Aliphatic Amines

Journal

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 137, Issue 18, Pages 6053-6058

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/jacs.5b02218

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Funding

  1. Federal Ministry of Education and Research (BMBF)
  2. Evonik Industries
  3. Shanghai Institute of Organic Chemistry-Zhejiang Medicine

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Hydroamidation of olefins constitutes an ideal atom-efficient method to prepare Carboxylic amides from easily available,olefins, CC, and amines. So far, aliphatic amines are not suitable for these transformations. Here we present a ligand- and additive-free Rh(I) catalyst as solution to This problem. Various amides are obtained in good yields and excellent regioselectivities. Notably, chemoselective amidation of aliphatic amines takes place in the presence Of aromatic amines and alcohols. Mechanistic-Studies reveal the presence of Rh-acyl species as crucial intermediates for the selectivity and rate-limiting step in the proposed Rh(I)-catalytic cycle.

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