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Gold-catalyzed cycloisomerization of 1,5-allenynes via dual activation of an ene reaction.

ABSTRACT: Tris(triphenylphosphinegold) oxonium tetrafluoroborate, [(Ph3PAu)3O]BF4, catalyzes the rearrangement of 1,5-allenynes to produce cross-conjugated trienes. Experimental and computational evidence shows that the ene reaction proceeds through a unique nucleophilic addition of an allene double bond to a cationic phosphinegold(I)-complexed phosphinegold(I) acetylide, followed by a 1,5-hydrogen shift.

SUBMITTER: Cheong PH

PROVIDER: S-EPMC2995695 | biostudies-literature | 2008 Apr

REPOSITORIES: biostudies-literature

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Gold-catalyzed cycloisomerization of 1,5-allenynes via dual activation of an ene reaction.

Cheong Paul Ha-Yeon PH Morganelli Philip P Luzung Michael R MR Houk K N KN Toste F Dean FD

Journal of the American Chemical Society 20080308 13

Tris(triphenylphosphinegold) oxonium tetrafluoroborate, [(Ph3PAu)3O]BF4, catalyzes the rearrangement of 1,5-allenynes to produce cross-conjugated trienes. Experimental and computational evidence shows that the ene reaction proceeds through a unique nucleophilic addition of an allene double bond to a cationic phosphinegold(I)-complexed phosphinegold(I) acetylide, followed by a 1,5-hydrogen shift. ...[more]

PMID: 18327944

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