Alcoholysis of Phosphaisocoumarins and Synthesis of 2-(2-Oxoalkyl)phenylphosphonates

作者：Peng, Ai Yun^*; Guo, Yu Juan; Ke, Zhi Hai; Zhu, Shizheng

来源：European Journal of Organic Chemistry, 2008, (31): 5277-5282.

DOI：10.1002/ejoc.200800616

• Alcoholysis
• Phosphonates
• Phosphorus heterocycles
• Hydration
• Alkynes

Phosphaisocoumarins do not undergo aminolysis, but instead they were found to be susceptible to alcoholysis in the presence of alcohols and primary amines. This paper examined this unexpected alcoholysis reaction and found that in the presence of Et3N or K2CO3, 4-unsubstituted- and 4-chlorophosphaisocoumarins under-went the alcoholysis reaction smoothly to give a series of 2-(2-oxoalkyl)phenylphosphonates in good yields, whereas 4-iodo- and 4-bromophosphaisocoumarins under-went a dehalogenation-alcoholysis tandem reaction. The possible mechanism for the alcoholysis reaction was discussed. In addition, direct access to 2-(2-oxoalkyl)phenylphosphonates was developed by the mercury(II)-catalyzed hydration of 2-(1-alkynly)phenylphosphonates with high regioselectivity. In a preliminary study, the obtained novel keto phosphonates showed medium inhibitory activity towards a-chymotrypsin.

• 出版日期2008-11
• 单位中国科学院; 中山大学