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Synlett 2010(19): 2879-2882  
DOI: 10.1055/s-0030-1259038
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Gold-Catalyzed Stereoselective Synthesis of Di- or Trisubstituted Olefins Possessing a 1,4-Diene Framework via Intramolecular Allylation of Alkynes

Yoshikazu Horino*, Yuichi Nakashima, Ken Hashimoto, Shigeyasu Kuroda*
Department of Applied Chemistry, Graduate School of Science and Engineering, University of Toyama, Gofuku 3190, Toyama, 930-8555, Japan
Fax: +81(76)4456819; e-Mail: horino@eng.u-toyama.ac.jp; e-Mail: kuro@eng.u-toyama.ac.jp;
Further Information

Publication History

Received 12 July 2010
Publication Date:
10 November 2010 (online)

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Abstract

The cationic gold(I)-catalyzed reaction of 1-alkynyl-2-allylsilylbenzenes with water results in intramolecular allylation of the alkynes via 7-exo-dig cyclization to give 1,4-dienes in good yield with excellent stereoselectivities.

Key words

catalysis - 1,4-dienes - allylation - allylsilanes - gold

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9

Use of phenol as a nucleophile in place of water gave a complex mixture.

14

AgNTf2, PtCl2, (PPh3)2PtCl2/2AgNTf2, and Sc(OTf)3 did not show any catalytic activities. Furthermore, background reaction mediated by Tf2NH did not proceed, either.

18

For details, see Supporting Information.

19

Another interesting alternative mechanism for the formation of 2, as suggested by one referee, involves initial formation of 3-allyl-1-silaindenes and their subsequent hydrolysis. Indeed, we have observed the formation of 2 from isolated 3-allyl-1-silaindenes under our reaction conditions. However, we were unable to detect such intermediates when monitoring the reaction of 1 by ¹H NMR spectroscopy (see Supporting Information for further details). Nevertheless, we would like to thank the referee for this suggestion.