A Density Functional Theory (DFT) Mechanistic Study of Gold(I)-Catalyzed Alkynylation of the Indole and Pyrrole Substrates, Using a Hypervalent Iodine Reagent
作者： Alireza Ariafard
DOI: 10.1021/CS500613T
关键词:
摘要: Density functional theory (DFT) was utilized to probe the mechanism of AuCl-catalyzed alkynylation indole and pyrrole substrates using a hypervalent iodine reagent ([(tri-iso-propysilyl)ethynyl]-1,2-benziodoxol-3(1H)-one (TIPS-EBX)). An unprecedented reaction shown be operative. In this mechanism, catalytic starts with coordination alkyne moiety iodine(III) AuCl catalyst, followed by transfer alkynyl group from IIII AuI. The center found capable activating triple bond more efficiently than gold(I) center. nucleophilic attack aromatic on IIII-activated gives vinyl complex. According calculations, step predicted rate-determining step. Starting complex, product is formed through interaction occupied σAu–C-orbital vacant σI–C*-orbital, very fast deprotonation reac...
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