Jia Kunfang, Li Junzhao, Chen Yiyun
State Key Laboratory of Bioorganic and Natural Products Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, P. R. China.
Chemistry. 2018 Mar 2;24(13):3174-3177. doi: 10.1002/chem.201800202. Epub 2018 Feb 5.
Herein the first P-C(sp ) bond cleavage and radical alkynylation of α-phosphorus alcohols to construct phosphonoalkynes is reported. The phosphorus radical is generated upon P-C bond cleavage reaction via the alkoxyl radical through photoredox catalysis with cyclic iodine(III) reagents. Various arylphosphinoyl-, alkylphosphinoyl-, phosphonate-, and phosphonic amide alcohols serve as radical phosphorus precursors to construct phosphonoalkynes for the first time.
本文报道了首例α-磷醇的P-C(sp³)键断裂及自由基炔基化反应，用于构建膦炔。通过光氧化还原催化，利用环状碘(III)试剂，在P-C键断裂反应中经由烷氧基自由基生成磷自由基。首次使用各种芳基次膦酰基、烷基次膦酰基、膦酸酯和膦酰胺醇作为自由基磷前体来构建膦炔。
