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DFT Studies of Dimerization Reactions of Boroles
Author(s) -
Wang Zheng,
Zhou Yu,
Lee KaHo,
Lam Wai Han,
Dewhurst Rian D.,
Braunschweig Holger,
Marder Todd B.,
Lin Zhenyang
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201701737
Subject(s) - substituent , chemistry , steric effects , dimer , aryl , density functional theory , carbon atom , stereochemistry , computational chemistry , ring (chemistry) , organic chemistry , alkyl
Abstract Boroles undergo dimerization reactions to give Diels–Alder (DA) dimers, bridged‐bicyclic (BB) dimers or spiro dimers (SD) depending on the substituents on the borole. We performed DFT calculations to investigate how different substituents at the carbon atoms of the butadiene backbone as well as at the boron atom influence the dimerization reaction pathways. The DFT results show that, in general, both the DA and BB dimers are easily accessible kinetically, and the DA dimers are thermodynamically more stable than the BB dimers. When the substituent–substituent repulsive steric interactions are alleviated to a certain extent, the BB dimers are more stable than the DA dimer, and become accessible. The SD dimers are generally kinetically difficult to obtain. However, we found that aryl substituents promote the formation of the SD dimers.