Premium
N‐Aryl Groups Are Ubiquitous in Cross‐Dehydrogenative Couplings Because They Stabilize Reactive Intermediates
Author(s) -
Tsang Althea S.K.,
Hashmi A. Stephen K.,
Comba Peter,
Kerscher Marion,
Chan Bun,
Todd Matthew H.
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.201700430
Subject(s) - aryl , substituent , reactive intermediate , chemistry , combinatorial chemistry , mechanism (biology) , computational chemistry , photochemistry , computer science , stereochemistry , organic chemistry , physics , catalysis , alkyl , quantum mechanics
Abstract The mechanism of cross‐dehydrogenative coupling (CDC) reactions has been examined by experimental and computational methods. We provide a rationale for the ubiquity of the N ‐aryl group in these reactions. The aryl substituent stabilizes two intermediates and the high‐energy transition state that connects them, which together represent the rate‐determining step. This knowledge has enabled us to predict whether new CDC substrates will react either well or poorly.