Highly active Au(I) catalyst for the intramolecular exo-hydrofunctionalization of allenes with carbon, nitrogen, and oxygen nucleophiles.

Published

Journal Article

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 degrees 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. gamma-Hydroxy and delta-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.

Full Text

Duke Authors

Cited Authors

  • Zhang, Z; Liu, C; Kinder, RE; Han, X; Qian, H; Widenhoefer, RA

Published Date

  • July 2006

Published In

Volume / Issue

  • 128 / 28

Start / End Page

  • 9066 - 9073

PubMed ID

  • 16834380

Pubmed Central ID

  • 16834380

Electronic International Standard Serial Number (EISSN)

  • 1520-5126

International Standard Serial Number (ISSN)

  • 0002-7863

Digital Object Identifier (DOI)

  • 10.1021/ja062045r

Language

  • eng