4.8 Article

Enantioselective Addition of Pyrazoles to Dienes**

Journal

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 60, Issue 36, Pages 19660-19664

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202105679

Keywords

1; 3-diene; enantioselectivity; hydroamination; Pd-catalysis; pyrazole

Funding

  1. UC Irvine
  2. National Institutes of Health [1R35GM127071]
  3. National Science Foundation [CHE-1465263]

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This study presents the first enantioselective addition of pyrazoles to 1,3-dienes, resulting in the formation of secondary and tertiary allylic pyrazoles with excellent regioselectivity. Mechanistic studies indicate a distinct pathway involving Pd-0-catalyzed ligand-to-ligand hydrogen transfer (LLHT), expanding the field of diene hydrofunctionalization with tolerance for various functional groups.
We report the first enantioselective addition of pyrazoles to 1,3-dienes. Secondary and tertiary allylic pyrazoles can be generated with excellent regioselectivity. Mechanistic studies support a pathway distinct from previous hydroaminations: a Pd-0-catalyzed ligand-to-ligand hydrogen transfer (LLHT). This hydroamination tolerates a range of functional groups and advances the field of diene hydrofunctionalization.

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