On the Mechanism of the Digold(I)-Hydroxide-Catalysed Hydrophenoxylation of Alkynes
作者： Adrián Gómez-Suárez , Yoshihiro Oonishi , Anthony R. Martin , Sai V. C. Vummaleti , David J. Nelson
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摘要: Herein we present a detailed investigation of the mechanistic aspects dual gold-catalysed hydrophenoxylation alkynes, using both experimental and computational methods. The dissociation [{Au(NHC)}2(µ-OH)][BF4] is essential to enter catalytic cycle; this step favored in presence bulky, non-coordinating counterions. Moreover, silico studies confirmed that phenol does not only act as reactant, but co-catalyst, lowering energy barriers for several transition states. A gem-diaurated species might form during reaction, lies deep within potential well, likely be an ‘off-cycle’ rather than ‘in-cycle’ intermediate.
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