Rhodium-Catalyzed Intramolecular, Anti-Markovnikov Hydroamination. Synthesis of 3-Arylpiperidines

Akihiro Takemiya and John F. Hartwig*
Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 06520-8107
J. Am. Chem. Soc., 2006, 128 (18), pp 6042–6043
DOI: 10.1021/ja058299e
Publication Date (Web): April 12, 2006
Copyright © 2006 American Chemical Society
*

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

, john.hartwig@yale.edu

Abstract

Abstract Image

The intramolecular anti-Markovnikov hydroamination of 1-(3-aminopropyl)vinylarenes in the presence of a readily available rhodium catalyst to form 3-arylpiperidines is reported. In contrast to intermolecular hydroamination of vinylarenes, which occurred in high yields in the presence of rhodium catalysts containing DPEphos, the intramolecular reaction occurred in high yield in the presence of [Rh(COD)(DPPB)]BF4 as catalyst. Reactants with substituents β to the nitrogen occurred in high yield, and these reactions formed 3,5-disubstituted piperidines with high diastereomeric excess. The regiochemistry of these cyclizations contrasts with the regiochemistry of intramolecular hydroaminations catalyzed by lanthanide complexes, group III metal complexes, and platinum complexes, all of which have been reported to form cyclization products from Markovnikov addition.

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History

  • Published In Issue May 10, 2006
  • Received December 6, 2005

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