| Quinoline, isoquinoline, phosphate, xanthene and their derivatives have important biological and pharmacological activity, which are widely used in the synthesis of natural products and pharmaceutical intermediates. Therefore, the organic chemists get great interest in these compounds.Benzyne is a highly active intermediate in organic synthesis. The high electrophlilcity of benzyne enables it to be widely used in the field of synthetic organic chemistry and the synthesis of natural products. This paper mainly carried out based on the insertion-cyclization reaction of benzyne. The main contents include three parts as follows:1. "One-pot" preparation of dearomatic phosphonylated heterocycles. 2-(trimethylsilyl) phenyl trifluoromethanesulfonate, as the precursor of benzyne, underwent the effect of fluoride ions to generate benzyne in situ, and then dearomatic phosphonylated heterocycles were prepared through inserting-cyclization reaction of benzyne with quinoline, isoquinoline and phosphite. 21 kinds of different substituted dearomatic phosphonylated heterocycles were obtained under the optimization of reaction condition to give 50%-90% yields. By further analysis of the experimental results proposed reaction mechanism was presented that fluoride ions catalyzed benzyne reacting with quinoline, isoquinoline and phosphite to obtain different substituted dearomatic phosphonylated heterocycles.2. "One-pot" preparation of dearomatic chlorinated heterocycles. 2-(trimethylsilyl) phenyl trifluoromethanesulfonate, as the precursor of benzyne, underwent the effect of fluoride ions to generate benzyne in situ, and then dearomatic chlorinated heterocycles were prepared through inserting-cyclization reaction of benzyne with quinoline, isoquinoline and dichloromethane, trichloromethane. 17 kinds of different substituted dearomatic chlorinated heterocycles were obtained under the optimization of reaction condition to give 45%-86% yields.3. Cycloannulation of o-quinone methides with benzyne. 2-(trimethylsilyl) phenyl trifluoromethanesulfonate, as the precursor of benzyne, underwent the effect of fluoride ions to generate benzyne in situ, and then cycloannulation of o-quinone methides with benzyne. Currently 9 kinds of different substituted cycloannulation of o-quinone methides with benzyne were obtained under the optimization of reaction condition to give 54%-89% yields.In summary, based on insertion-cyclization reaction of benzyne, the new method of synthesis benzoheterocyclic compouds such as dearomatic phosphonylated heterocycles, dearomatic chlorinated heterocycles and cycloannulation of o-quinone methides with benzyne had been developed; and the application of benzyne had also been expanded. |
