Highly Active Au(I) Catalyst for the Intramolecular exo-Hydrofunctionalization of Allenes with Carbon, Nitrogen, and Oxygen Nucleophiles

Zhibin Zhang, Cong Liu, Robert E. Kinder, Xiaoqing Han, Hua Qian, and Ross A. Widenhoefer*
Contribution from the P. M. Gross Chemical Laboratory, Duke University, Durham, North Carolina 27708-0346
J. Am. Chem. Soc., 2006, 128 (28), pp 9066–9073
DOI: 10.1021/ja062045r
Publication Date (Web): June 20, 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.

, rwidenho@chem.duke.edu

Abstract

Abstract Image

Reaction of benzyl (2,2-diphenyl-4,5-hexadienyl)carbamate (4) with a catalytic 1:1 mixture of Au[P(t-Bu)2(o-biphenyl)]Cl (2) and AgOTf (5 mol %) in dioxane at 25 °C for 45 min led to isolation of benzyl 4,4-diphenyl-2-vinylpyrrolidine-1-carboxylate (5) in 95% yield. The Au(I)-catalyzed intramolecular hydroamination of N-allenyl carbamates tolerated substitution at the alkyl and allenyl carbon atoms and was effective for the formation of piperidine derivatives. γ-Hydroxy and δ-hydroxy allenes also underwent Au-catalyzed intramolecular hydroalkoxylation within minutes at room temperature to form the corresponding oxygen heterocycles in good yield with high exo-selectivity. 2-Allenyl indoles underwent Au-catalyzed intramolecular hydroarylation within minutes at room temperature to form 4-vinyl tetrahydrocarbazoles in good yield. Au-catalyzed cyclization of N-allenyl carbamates, allenyl alcohols, and 2-allenyl indoles that possessed an axially chiral allenyl moiety occurred with transfer of chirality from the allenyl moiety to the newly formed stereogenic tetrahedral carbon atom.

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History

  • Published In Issue July 19, 2006
  • Received March 24, 2006

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