Work

Water‐Catalytic Deconstructive and Proton Transfer Cyclopropanation of Sulfoxonium Ylide with Olefin

Year: 2025

Type: article

Abstract: Cyclopropane rings, with their distinct structure and reactivity, have long been a focus in organic chemistry and are significant pharmacophores in medicinal chemistry. Conventional direct cyclopropanation methods for olefins do not modify the functional groups on the α- or β-carbon of olefins. Herein, a novel deconstructive cyclopropanation reaction is designed for olefins using a close-open-close ring strategy. This enables the migration of functional groups to the α- or β-carbon of olefins, leading to the formation of regioselective cyclopropane compounds, which is a previously unreported approach. By exploiting the zwitterionic property of sulfoxonium ylides and combining them with Density Functional Theory (DFT) computations, the reaction is proposed to proceed via a [2 + 2] cycloaddition to form a strained cyclobutene intermediate, followed by cyclobutane ring-opening and nucleophilic substitution through a water-involved proton-shuttle process for ring closure. Hydrogen-bonding interactions play a significant role in controlling the regioselectivity.

Source: Advanced Science

DOI: 10.1002/advs.202502430

Authors: Xianglin Yu, Liuting Huang, Haiyue Yang, Lijuan Song, Yi Jin

Institutions: Yunnan University, Harbin Institute of Technology

Language: English

Topic: Cyclopropane Reaction Mechanisms

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: gold

Estimated APC paid: $6,730

Funders: National Natural Science Foundation of China, Natural Science Foundation of Guangdong Province, Yunnan University, Shenzhen Bay Laboratory