biostudies-literatureYu XLeading Talent Project of Innovation of Double Thousand Plan in Jiangxi ProvinceYunnan Fundamental Research ProjectsNSFCProject of Innovative Research Team of Yunnan ProvinceNational Natural Science Foundation of ChinaNatural Science Foundation of Guangdong Provincee02430https://www.ebi.ac.uk/biostudies/studies/S-EPMC12376613biostudies-literatureUnknown12(31)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.Advanced science (Weinheim, Baden-Wurttemberg, Germany)Water-Catalytic Deconstructive and Proton Transfer Cyclopropanation of Sulfoxonium Ylide with Olefin.PMC12376613S2021DQKJ219522267021202405AS350010202401BF070001-021222030232022A1515011859Yang HSong LHuang LJin YYu XfalseWater-Catalytic Deconstructive and Proton Transfer Cyclopropanation of Sulfoxonium Ylide with Olefin.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.2025-01-01T00:00:00Z2025 Aug2026-05-09T19:05:34.388Z2026-04-08T01:10:37.674ZS-EPMC123766134044458810.1002/advs.202502430