†Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein Str. 29a, 18059 Rostock, Germany.
‡Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne, 1015 Lausanne, Switzerland.
J Am Chem Soc. 2015 May 13;137(18):6053-8. doi: 10.1021/jacs.5b02218. Epub 2015 May 4.
Hydroamidation of olefins constitutes an ideal, atom-efficient method to prepare carboxylic amides from easily available olefins, CO, 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.
烯烃的氢甲酰胺化反应是一种理想的原子经济性方法，可从易得的烯烃、CO 和胺制备羧酸酰胺。到目前为止，脂肪胺不适合这些转化。在这里，我们提出了一种无配体和添加剂的 Rh(I)催化剂来解决这个问题。各种酰胺以良好的收率和优异的区域选择性得到。值得注意的是，在芳香胺和醇存在下，脂肪胺可以选择性地进行酰胺化。机理研究表明，Rh-酰基物种的存在是该 Rh(I)催化循环中选择性和速率限制步骤的关键中间体。
