三氟化硼及其硅胶负载物催化下酮类的Baeyer-Villiger氧化反应

Catalytic Baeyer-Villiger oxidation of ketones with boron trifluoride and its silica supported

考察了三氟化硼及其硅胶负载催化下30%H2O2对酮类的Baeyer-Villiger氧化反应.结果表明,两种催化剂都能在温和条件下催化酮类氧化得到相应的酯和内酯;小分子三氟化硼对2-金刚烷酮、环戊酮、2-甲基环己酮的催化氧化基本实现完全转化,产物内酯的选择性分别达到99%,99%和74%,其对链状的4-甲基-2-戊酮的氧化表现出较好的催化性能,相同条件下底物转化率和产物酯的选择性分别可达25%和99%;硅胶负载三氟化硼催化酮类Baeyer-Villiger氧化反应时,产物内酯的选择性很好,催化剂制备过程简单,并具有较好的重复使用性能.

Boron trifluoride etherate（BFs. OEt2）and silica supported BF3 are used as catalysts for Baeyer- Villiger oxidation of ketones with 30% hydrogen peroxide as oxidant. Many ketones are effectively oxidized to the corresponding esters or lactones under mild reaction conditions. 2-andamantanone, cyclopentanone, 2-rnethyl-cyclohexanone are efficiently oxidized to the corresponding lactones by boron trifluoride etherate（BFa ~ OEtz） with the product selectivity of 99%, 99% and 74%, respectively. The catalyst also shows catalytic acticity for the oxidation of 4-methyl-2-heptanone with the substrate conversion, as well as ester selectivity of 25% and 99%, respectively. The silica supported BFa affords high lactone＇s selectivity in Baeyer-Villiger oxidation of many ketones. It can be easily prepared and recycled in the oxidations.