Synergistic Catalysis by Brønsted Acid/Carbodicarbene Mimicking Frustrated Lewis Pair-Like Reactivity

Yi-Chen Chan; Yuna Bai; Wen-Ching Chen; Hsing-Yin Chen; Chen-Yu Li; Ying-Yann Wu; Mei-Chun Tseng; Glenn P A Yap; Lili Zhao; Hsuan-Ying Chen; Tiow-Gan Ong

doi:10.1002/anie.202107127

Synergistic Catalysis by Brønsted Acid/Carbodicarbene Mimicking Frustrated Lewis Pair-Like Reactivity

Angew Chem Int Ed Engl. 2021 Sep 1;60(36):19949-19956. doi: 10.1002/anie.202107127. Epub 2021 Jul 29.

Authors

Yi-Chen Chan^{1

2

3}, Yuna Bai⁴, Wen-Ching Chen¹, Hsing-Yin Chen⁵, Chen-Yu Li⁵, Ying-Yann Wu¹, Mei-Chun Tseng¹, Glenn P A Yap⁶, Lili Zhao⁴, Hsuan-Ying Chen^{5

7}, Tiow-Gan Ong^{1

8}

Affiliations

¹ Institute of Chemistry, Academia Sinica, Taipei, Taiwan, R.O.C.
² Department of Applied Chemistry, National Yang Ming Chiao Tung University, Hsinchu, Taiwan, R.O.C.
³ Taiwan International Graduate Program (TIGP), Sustainable Chemical Science and Technology (SCST), Academia Sinica, Taipei, Taiwan, R.O.C.
⁴ Institute of Advanced Synthesis, School of Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing, China.
⁵ Department of Medicinal and Applied Chemistry, Drug Development and Value Creation Research Center, Kaohsiung Medical University, Kaohsiung, 80708, Taiwan, R.O.C.
⁶ The Department of Chemistry and Biochemistry, University of Delaware, Newark, DE, USA.
⁷ Department of Medicinal Research, Kaohsiung Medical University Hospital, Kaohsiung, 80708, Taiwan, R.O.C.
⁸ Department of Chemistry, National (Taiwan) University, Taipei, Taiwan, R.O.C.

PMID: 34128303
DOI: 10.1002/anie.202107127

Abstract

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.

Keywords: BnOH; benzyl alcohol; carbodicarbene; frustrated Lewis pair.

Abstract

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