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Mechanistic insight into the rhodium(III)‐catalyzed ortho‐selective coupling of diverse arenes with 4‐acyl‐1‐sulfonyltriazoles: A computational study
Author(s) -
Wu Weirong,
Liu Yue,
Hu Jiayi,
Xiong Jiageng,
Hou Hua
Publication year - 2020
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.26119
Subject(s) - rhodium , chemistry , catalysis , regioselectivity , limiting , kinetic isotope effect , acetic acid , activation barrier , computational chemistry , density functional theory , coupling (piping) , medicinal chemistry , stereochemistry , combinatorial chemistry , organic chemistry , deuterium , mechanical engineering , physics , quantum mechanics , engineering
Abstract A mechanistic study of the Cp*Rh(III)‐catalyzed annulative coupling of benzimidates with 4‐acyl‐1‐sulfonyltriazoles by CH activation was performed using density functional M06 method. It was demonstrated that the active catalyst during the coupling process should be the cation [Cp*Rh(OAc)] + rather than the neutral Cp*Rh(OAc) 2 and Zn(OAc) 2 as proposed previously by the experimenters. A novel energetically feasible reaction pathway has been revealed theoretically in details. The acetic acid‐mediated cyclization process was confirmed to be the rate‐limiting step with an overall barrier of 24.3 kcal/mol, excluding any importance of the CH cleavage mechanism as supported by the kinetic isotope effect experiments. The major factors responsible for the preferred regioselectivity of N ‐pyrimidinylinoles with 4‐acetyl‐1‐sulfonyltriazoles were discussed.