Water‐Catalytic Deconstructive and Proton Transfer Cyclopropanation of Sulfoxonium Ylide with Olefin
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 olef...
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| Main Authors: | , , , , |
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| Format: | Article |
| Language: | English |
| Published: |
Wiley
2025-08-01
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| Series: | Advanced Science |
| Subjects: | |
| Online Access: | https://doi.org/10.1002/advs.202502430 |
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| Summary: | 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. |
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| ISSN: | 2198-3844 |