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Updated: May 19, 2026

Preparation and Use of Carbonyl-decorated Carbenes in the Activation of White Phosphorus
Published on: October 3, 2014
Photoinduced Deoxygenative Halocarbocyclization of Aldehyde Enabled by Tertiary Phosphine
Xuemei Zhang1, Yan Bai1, Ran Xue1
1Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, College of Chemistry and Materials Science, Zhejiang Normal University, Jinhua 321004, China.
Abstract:
The development of transition-metal-free protocols for the deoxygenative difunctionalization of carbonyls represents a significant challenge in organic synthesis. Herein, we report a photochemical strategy for deoxygenative difunctionalization of γ-enal by leveraging the reactivity of phosphine-iodide EDA complexes. Mechanistic studies indicate that the reaction proceeds through single-electron transfer within EDA complexes, addition of the fluoroalkyl radical to a C═C bond, 5-exo-trig cyclization, radical-radical cross-coupling between an in situ-generated alkoxy radical and phosphine radical cation, and SN2 substitution. This method features a broad substrate scope and high step economy, offering a robust platform for the rapid assembly of complex functionalized carbocycles.
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