Selective Carbonyl−C(sp3) Bond Cleavage To Construct Ynamides, Ynoates, and Ynones by Photoredox Catalysis. (25th January 2017)

• Record Type: Journal Article
• Authors: Jia, Kunfang; Pan, Yue; Chen, Yiyun
• Is Part Of: Angewandte Chemie. Volume 129:Number 9(2017)
• Page Start: 2518
• Page End: 2521
• Publication Date: 2017-01-25
• Subjects: Acylverbindungen -- Hypervalente Verbindungen -- Photochemie -- Radikale -- Reaktionsmechanismen; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201611897
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: Carbon–carbon bond cleavage/functionalization is synthetically valuable, and selective carbonyl−C(sp 3 ) bond cleavage/alkynylation presents a new perspective in constructing ynamides, ynoates, and ynones. Reported here is the first alkoxyl‐radical‐enabled carbonyl−C(sp 3 ) bond cleavage/alkynylation reaction by photoredox catalysis. The use of novel cyclic iodine(III) reagents are essential for β‐carbonyl alkoxyl radical generation from β‐carbonyl alcohols, including alcohols with high redox potential ( E p ox >2.2 V vs. SCE in MeCN). β‐Amide, β‐ester, and β‐ketone alcohols yield ynamides, ynoates, and ynones, respectively, for the first time, with excellent regio‐ and chemoselectivity under mild reaction conditions.