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Synergistic Catalysis by Brønsted Acid/Carbodicarbene Mimicking Frustrated Lewis Pair‐Like Reactivity
Author(s) -
Chan YiChen,
Bai Yuna,
Chen WenChing,
Chen HsingYin,
Li ChenYu,
Wu YingYann,
Tseng MeiChun,
Yap Glenn P. A.,
Zhao Lili,
Chen HsuanYing,
Ong TiowGan
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202107127
Subject(s) - reactivity (psychology) , frustrated lewis pair , chemistry , lone pair , catalysis , nucleophile , lewis acids and bases , benzyl alcohol , stacking , polymerization , photochemistry , organic chemistry , molecule , polymer , medicine , alternative medicine , pathology
Carbodicarbene (CDC), unique carbenic entities bearing two lone pairs of electrons are well‐known for their strong Lewis basicity. We demonstrate herein, upon introducing a weak Brønsted acid benzyl alcohol (BnOH) as a co‐modulator, CDC is remolded into a Frustrated Lewis Pair (FLP)‐like reactivity. DFT calculation and experimental evidence show BnOH loosely interacting with the binding pocket of CDC via H‐bonding and π‐π stacking. Four distinct reactions in nature were deployed to demonstrate the viability of proof‐of‐concept as synergistic FLP/Modulator (CDC/BnOH), demonstrating enhanced catalytic reactivity in cyclotrimerization of isocyanate, polymerization process for L ‐lactide (LA), methyl methacrylate (MMA) and dehydrosilylation of alcohols. Importantly, the catalytic reactivity of carbodicarbene is uniquely distinct from conventional NHC which relies on only single chemical feature of nucleophilicity. This finding also provides a new spin in diversifying FLP reactivity with co‐modulator or co‐catalyst.