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Importance of Counterions in Gold‐hydrogen Bonding Cooperative Catalytic Approach to Spirocyclic Rings: Insights on Mechanism and Origins
Author(s) -
Li Yunhe,
Zhao Xiang
Publication year - 2020
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.202001303
Subject(s) - chemoselectivity , hydrogen bond , intramolecular force , catalysis , counterion , mechanism (biology) , chemistry , conjugated system , reaction mechanism , combinatorial chemistry , computational chemistry , stereochemistry , organic chemistry , ion , molecule , polymer , philosophy , epistemology
The detailed mechanism and origins of gold‐catalyzed intramolecular dearomatization of naphthols to spirocarbocycles are systematically studied. Specifically, the hydrogen‐bonding mediated cooperative Brønsted‐acid catalysis mechanism was the most plausible mechanism for dearomatization to spirocarbocycles because of its intricate interplay between hydrogen bonds and conjugated π systems in the spirointermediates. Three activation modes are established, and the important role of counterion via hydrogen bonding in determining the experimentally observed chemoselectivity is well rationalized by our calculations.