The Stannum-Ene Reactions of Benzyne and Cyclohexyne with Superb Chemoselectivity for Cyclohexyne

Lianggui Li; Chunhui Shan; Jiarong Shi; Wensheng Li; Yu Lan; Yang Li

doi:10.1002/anie.202117351

The Stannum-Ene Reactions of Benzyne and Cyclohexyne with Superb Chemoselectivity for Cyclohexyne

Angew Chem Int Ed Engl. 2022 Apr 19;61(17):e202117351. doi: 10.1002/anie.202117351. Epub 2022 Feb 28.

Authors

Lianggui Li¹, Chunhui Shan^{1

2}, Jiarong Shi¹, Wensheng Li³, Yu Lan^{1

4}, Yang Li^{1

5}

Affiliations

¹ School of Chemistry and Chemical Engineering, Chongqing University, 174 Shazheng St., Chongqing, 400030, P. R. China.
² College of Chemistry, Chongqing Normal University, Chongqing, 401331, P. R. China.
³ College of Chemistry and Chemical Engineering, Chongqing University of Technology, Chongqing, 400054, P. R. China.
⁴ Green Catalysis Center and College of Chemistry, Zhengzhou University, Zhengzhou, Henan, 450001, P. R. China.
⁵ College of Chemistry, Jilin University, Changchun, 130012, P. R. China.

PMID: 35170157
DOI: 10.1002/anie.202117351

Abstract

The stannum-ene reactions of both benzyne and cyclohexyne were realized, which is particularly suitable for cyclohexyne with a broad substrate scope and excellent chemoselectivity. Our DFT calculations via distortion/interaction analysis revealed that both stannum- and hydrogen-ene reactions with cyclohexyne have later transition states due to their higher distortion energies in the transition states than those in benzyne reactions, which lead to enhanced Pauli repulsion as the decisive factor in the interaction energy accompanied with enlarged energy gap between two types of ene reactions. Therefore, excellent chemoselectivity was disclosed in the cyclohexyne-ene reaction.

Keywords: Benzyne; Chemoselectivity; Cyclohexyne; Distortion-Interaction Analysis; Stannum-Ene Reaction.

Publication types

Research Support, Non-U.S. Gov't

MeSH terms

Benzene Derivatives*
Tin*

Substances

Benzene Derivatives
benzyne
Tin