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Gold-Catalyzed Cycloisomerization of 1,6-Diyne Esters to 1H‑Cyclopenta[b]naphthalenes, cis-Cyclopenten-2-yl δ‑Diketones, and Bicyclo[3.2.0]hepta-1,5-dienes

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journal contribution
posted on 05.12.2014, 00:00 by Dan Li, Weidong Rao, Guan Liang Tay, Benjamin James Ayers, Philip Wai Hong Chan
A synthetic method to chemoselectively prepare 1H-cyclopenta­[b]­naphthalenes, cis-cyclopenten-2-yl δ-diketones, and bicyclo[3.2.0]­hepta-1,5-dienes efficiently by gold-catalyzed cycloisomerization of 1,6-diyne esters is described. These three product classes were accessed divergently by taking advantage of the electronic and steric differences between a phosphine and NHC (NHC = N-heterocyclic carbene) ligand in the respective gold­(I) complexes and that of gold­(III) complex combined with substrate substitution patterns and optimized reaction conditions. In the presence of [PhCNAuIPr]+SbF6 (IPr = 1,3-bis­(2,6-diisopropylphenyl)­imidazol-2-ylidine) as the catalyst, substrates with a pendant aryl group at the acetate alkynyl position were found to undergo preferential 1,3-acyloxy migration/5-exo-dig cyclization/Friedel–Crafts reaction to give 1H-cyclopenta­[b]­naphthalenes. In contrast, the analogous reactions with PicAuCl2 (Pic =2-picolinate) were found to proceed by selective 1,3-acyloxy migration/5-exo-dig cyclization/1,5-acyl migration to afford cis-cyclopenten-2-yl δ-diketones. Changing the catalyst to [MeCNAu­(JohnPhos)]+SbF6 (JohnPhos = (1,1′-biphenyl-2-yl)-di-tert-butylphosphine) and the acetate alkynyl position from an aryl to vinyl substituent in the starting ester led to 1,3-acyloxy migration/5-exo-dig cyclization/Prins-type [2 + 2]-cycloaddition to provide bicyclo[3.2.0]­hepta-1,5-dienes.