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Ruthenium-catalyzed rearrangement of cis-1-ethynyl-2-vinyloxiranes to substituted phenols
Journal article   Peer reviewed

Ruthenium-catalyzed rearrangement of cis-1-ethynyl-2-vinyloxiranes to substituted phenols

Shambabu Joseph Maddirala, Arjan Odedra, Bhanu Pratap Taduri and Rai-Shung Liu
Synlett, (8), pp.1173-1176
15/05/2006

Abstract

1,2-hydrogen shift 2,6-disubstituted phenols cis-1-ethynyl-2-vinyloxiranes endo-dig cyclization Ruthenium-vinylidine intermediate TpRuPPh 3(CH3CN)2PF6
Catalytic cyclization of cis-1-ethynyl-2-vinyloxiranes was implemented with TpRuPPh 3 (CH 3 CN) 2 PF 6 catalyst (10 mol%), to give 2,6-disubstituted phenols in reasonable yields. Under similar conditions, 1,1,2,2-tetrasubstituted oxirane gave the 2,3,6-trisubstituted phenol with skeleton reorganization. On the basis of 2 H- and l3 C-labeling results, we propose that the reaction mechanism involves electrocyclization of ruthenium-vinylidene intermediate with cleavage of the carbon-oxygen bond of the epoxide. © Georg Thieme Verlag Stuttgart.

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