Development and Mechanistic Investigations of Enantioselective Pd-Catalyzed Intermolecular Hydroaminations of Internal Dienes

Journal Article (Journal Article)

We report the development of highly enantio- and regioselective Pd-catalyzed intermolecular hydroaminations of challenging 1,4-disubstituted acyclic dienes. Several aryl/alkyl-disubstituted dienes and a sterically differentiated alkyl/alkyl-disubstituted diene undergo coupling with a variety of secondary aliphatic amines, indoline, and primary anilines to generate allylic amines with myriad α-alkyl groups in up to 78% yield, >98:2 rr, and 98.5:1.5 er. A number of experiments, including deuterium labeling and transamination studies, shed light on mechanistic details of the reaction, such as the reversibility of individual steps of the proposed catalytic cycle and of the reaction as a whole.

Full Text

Duke Authors

Cited Authors

  • Park, S; Malcolmson, SJ

Published Date

  • September 7, 2018

Published In

Volume / Issue

  • 8 / 9

Start / End Page

  • 8468 - 8476

Electronic International Standard Serial Number (EISSN)

  • 2155-5435

Digital Object Identifier (DOI)

  • 10.1021/acscatal.8b01914

Citation Source

  • Scopus