"On-water" defluorophosphorylation of trifluoromethylated enones with phosphine oxides

被引：15

作者：

Chu, Xue-Qiang ^{[1
]}

Sun, Li-Wen ^{[1
]}

Ma, Cheng ^{[4
]}

Chen, Jia-Wei ^{[1
]}

Chen, Yu-Lan ^{[1
]}

Ni, Shao-Fei ^{[4
]}

Zhu, Ming-Quan ^{[1
]}

Zhou, Jie ^{[2
]}

Ma, Mengtao ^{[3
]}

Shen, Zhi-Liang ^{[1
]}

机构：

[1] Nanjing Tech Univ, Tech Inst Fluorochemistry TIF, Inst Adv Synth, Sch Chem & Mol Engn, Nanjing 211816, Peoples R China

[2] Nanjing Tech Univ, Coll Biotechnol & Pharmaceut Engn, State Key Lab Mat Oriented Chem Engn, Nanjing 211816, Peoples R China

[3] Nanjing Forestry Univ, Coll Sci, Dept Chem & Mat Sci, Nanjing 210037, Peoples R China

[4] Shantou Univ, Dept Chem, Key Lab Preparat & Applicat Ordered Struct Mat Gua, Shantou 515063, Peoples R China

来源：

GREEN CHEMISTRY | 2023年 / 25卷 / 16期

基金：

中国国家自然科学基金;

关键词：

DIAZO-COMPOUNDS; DEFLUORINATIVE ALKYLATION; BROOK REARRANGEMENT; CATALYST-FREE; EFFICIENT; DIFLUOROCARBENE; CONSTRUCTION; GENERATION; CHEMISTRY;

D O I：

10.1039/d3gc01565c

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The distinctive fluorine effects on "on-water" chemistry have remained less explored. In this work, an "on-water" reaction of & beta;-trifluoromethylated enones with phosphine oxides was developed for the preparation of highly functionalized gem-difluorodienes with excellent Z-selectivity. The reaction occurred through a well-designed tandem phospha-Brook rearrangement and defluorination sequence under transition-metal-free conditions in water solution, which efficiently overcame some competitive side reactions, such as hydrodefluorination, 1,4-nucleophilic addition, and phosphorylation. The success was attributed to favorable H-bonding interactions at the water-organic phase boundary which could activate the substrates and enhance the reaction selectivity.

引用

页码：6489 / 6497

页数：9

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