Zhang Li, Fang Yewen, Jin Xiaoping, Xu Housan, Li Ruifeng, Wu Hao, Chen Bin, Zhu Yiming, Yang Yi, Tian Zongming
College of Chemistry and Chemical Engineering, Taiyuan University of Technology, No. 79 West Yingze Street, Taiyuan 030024, China.
Org Biomol Chem. 2017 Oct 31;15(42):8985-8989. doi: 10.1039/c7ob02267k.
A general and robust protocol for the synthesis of terminal α-substituted vinylphosphonates via Suzuki coupling of α-bromovinylphosphonates with organotrifluoroborates has been successfully developed. This method features a broad substrate scope, great functional group compatibilities, and easy scale-up ability. In addition to easy access of nucleophiles, a straightforward synthesis of electrophiles was also realized with diethyl α-bromoethenylphosphonate as the starting material. With a combination of Pd(dba)/SPhos as the catalyst, a range of α-alkyl, aryl, heteroaryl, and alkynyl substituted ethenylphosphonates could be nicely accessed under mild conditions. As a synthetic application, the terminal vinylphosphonate was utilized as an effective Michael acceptor in the visible-light-promoted Giese reaction.
通过α-溴代乙烯基膦酸酯与有机三氟硼酸盐的铃木偶联反应，成功开发了一种通用且稳健的合成末端α-取代乙烯基膦酸酯的方法。该方法具有底物范围广、官能团兼容性好、易于放大的特点。除了亲核试剂易于获得外，还以α-溴代乙烯基膦酸二乙酯为起始原料实现了亲电试剂的直接合成。以Pd(dba)/SPhos为催化剂，在温和条件下可以顺利得到一系列α-烷基、芳基、杂芳基和炔基取代的乙烯基膦酸酯。作为一种合成应用，末端乙烯基膦酸酯在可见光促进的吉斯反应中用作有效的迈克尔受体。
