Department of Chemistry, Kangwon National University, Chuncheon 200-701 (Republic of Korea), Fax: (+82) 33-253-7582.
Chemistry. 2013 Nov 25;19(48):16461-8. doi: 10.1002/chem.201302652. Epub 2013 Oct 10.
Rhodium-catalyzed cyclization of phosphinic acids and phosphonic monoesters with alkynes has been developed. The oxidative annulation proceeds with complete conversion of phosphinic acid derivatives and allowed the atom-economic preparation of useful phosphaisocoumarins with high yield and selectivity. The reaction is tolerant of extensive substitution on the phosphinic acid, phosphonic monoester and alkyne, including halides, ketone, and hydroxyl groups as substituents. Furthermore, we found that alkenylphosphonic monoesters proceed to give a wide range of phosphorus 2-pyrones through oxidative annulation with alkynes. Mechanistic studies revealed that C-H bond metalation was the rate-limiting step.
铑催化膦酸和膦酸单酯与炔烃的环化反应已经被开发出来。该氧化环化反应以膦酸衍生物的完全转化为特征，并允许原子经济性地以高产率和选择性制备有用的磷异香豆素。该反应对膦酸、膦酸单酯和炔烃上的广泛取代基具有耐受性，包括卤化物、酮和羟基作为取代基。此外，我们发现烯基膦酸单酯通过与炔烃的氧化环化反应得到了一系列广泛的磷 2-吡喃酮。机理研究表明 C-H 键金属化是限速步骤。
