Affiliation:
1. Dalian National Laboratory for Clean Energy Dalian Institute of Chemical Physics Chinese Academy of Sciences Dalian 116023 Liaoning China
2. School of Chemistry and Chemical Engineering Key Laboratory of Surface & Interface Science of Polymer Materials of Zhejiang Province Zhejiang Sci-Tech University Hangzhou 310018 China
3. Leibniz-Institut für Katalyse e.V. Albert-Einstein-Straße 29a 18059 Rostock Germany
Abstract
AbstractGiven the prevalence of amide backbones in marketed pharmaceuticals and their ubiquity as critical binding units in natural peptides and proteins, it remains important to develop novel methods to construct amide bonds. We report here a general method for the anti‐Markovnikov hydroaminocarbonylation of unactivated alkenes under mild conditions, using copper catalysis in combination with hydroxylamine electrophile reagents and poly(methylhydrosiloxane) (PMHS) as a cheap and environmentally friendly hydride source. The reaction tolerates a variety of functional groups and efficiently converts unactivated terminal alkenes, 1,1‐disubstituted alkenes, and cyclic alkenes to the corresponding amides with exclusive anti‐Markovnikov selectivity (and high enantioselectivities/diastereoselectivities). Additionally, with minimal modification of the reaction conditions, alkynes can also undergo tandem hydrogenation‐hydroaminocarbonylation to alkyl amides.
Funder
K. C. Wong Education Foundation
China Postdoctoral Science Foundation