title: Selective Carbonyl-C(sp3) Bond Cleavage To Construct Ynamides, Ynoates, and Ynones by Photoredox Catalysis.
abstract: Carbon-carbon bond cleavage/functionalization is synthetically valuable, and selective carbonyl-C(sp3) bond cleavage/alkynylation presents a new perspective in constructing ynamides, ynoates, and ynones. Reported here is the first alkoxyl-radical-enabled carbonyl-C(sp3) 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 (Epox >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.
authors.affiliation: State Key Laboratory of Bioorganic and Natural Products Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, China.
authors.forename: Kunfang
authors.initials: K
authors.lastname: Jia
authors.affiliation: State Key Laboratory of Bioorganic and Natural Products Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, China.|Department of Chemistry, Shanghai University, 99 Shangda Road, Shanghai, 200444, China.
authors.forename: Yue
authors.initials: Y
authors.lastname: Pan
authors.affiliation: State Key Laboratory of Bioorganic and Natural Products Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, China.
authors.forename: Yiyun
authors.initials: Y
authors.lastname: Chen
keywords: acyl compounds; hypervalent compounds; photochemistry; radicals; reaction mechanisms