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Synthesis 2018; 50(01): 107-118
DOI: 10.1055/s-0036-1590904
DOI: 10.1055/s-0036-1590904
paper
One-Pot Synthesis of α,β-Unsaturated Esters, Ketones, and Nitriles from Alcohols and Phosphonium Salts
Financial support from the National Natural Science Foundation of China (No. 21302143 and 51572198) and Natural Science Foundation of Zhejiang Province (No. LY13B020006 and LZ17E020002) is greatly appreciated.Further Information
Publication History
Received: 17 July 2017
Accepted after revision: 10 August 2017
Publication Date:
12 September 2017 (online)
Abstract
A general method for the synthesis of α,β-unsaturated esters, ketones, and nitriles is successfully achieved by a one-pot copper-catalyzed oxidation with O2 in air as oxidant. The solvent mixture of acetonitrile and formamide (1:1) is optimized to ensure the oxidation of alcohols, deprotonation of phosphonium salt, and Wittig reaction occur efficiently in one pot. A broad range of substrates has been explored for this process, including three electron-withdrawing group (CO2Et, COPh, CN) functionalized phosphonium salts. They reacted not only with benzylic and heteroaromatic alcohols, but also with aliphatic alcohols, forming the corresponding α,β-unsaturated esters, ketones, and nitriles in moderate to excellent yields.
Key words
oxidation of alcohols - phosphonium salts - tandem reaction - copper catalyst - Wittig reaction - carbon–carbon double bondSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0036-1590904.
- Supporting Information
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For reviews on the copper-catalyzed oxidation of alcohols, see:
Cu/TEMPO catalyst systems: