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DFT Study on the Gold(I)‐Catalyzed Dehydrogenative Heterocyclization of 2 ‐( 1 ‐Alkynyl)‐ 2 ‐alken‐ 1 ‐ones to form 2,3 ‐Furan‐Fused Carbocycles: Effects of Additives C 5 H 5 NO vs. PhNO
Author(s) -
Yuan Binfang,
Chen Jinyang,
Wang Guangzhao,
Zhang Fulan,
Fang Luqiu,
Guo Xiaogang,
Huang Huisheng,
He Rongxing
Publication year - 2020
Publication title -
applied organometallic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.53
H-Index - 71
eISSN - 1099-0739
pISSN - 0268-2605
DOI - 10.1002/aoc.5443
Subject(s) - chemistry , catalysis , furan , deprotonation , protonation , proton , intramolecular force , medicinal chemistry , intermolecular force , reaction mechanism , computational chemistry , photochemistry , stereochemistry , organic chemistry , molecule , ion , physics , quantum mechanics
A computational study with the M06/B3LYP density functional is carried out to explore the effects of additives C 5 H 5 NO vs. PhNO on the gold‐catalyzed dehydrogenative heterocyclization of 2‐(1‐alkynyl)‐2‐alken‐1‐ones to form 2,3‐furan‐fused carbocycles. The following three conclusions are obtained based on our theoretical calculations. (a) The Au(I) catalyst plays a crucial role on the intramolecular cyclization reaction. (b) Both additives C 5 H 5 NO and PhNO as the proton shuttle can assist proton‐transfer through a two‐step proton‐transfer mechanism including the protonation of additive and the deprotonation of additive‐H + , whereas the catalytic capability of PhNO is weaker than that of C 5 H 5 NO (energy barrier: 90.6 vs. 33.2 kJ/mol). (c) C 5 H 5 NO‐H + has stronger stability comparing with PhNO‐H + because the basicity of C 5 H 5 NO is stronger than that of PhNO, which cause that the energy barrier of ts3 + PhNO‐H + (131.5 kJ/mol) is higher than that of ts3 + C 5 H 5 NO‐H + (60.5 kJ/mol) in the intermolecular addition. Therefore, the base strength is the primary factor that controls the catalytic capability of additives C 5 H 5 NO vs. PhNO. These studies are expected to improve our understanding of Au(I)‐catalyzed reactions involving additive as the cocatalyst and to provide guidance for the future design of new catalysts and new reactions.