o-Carboryne （1,2-dehydro-o-carborane） is a very useful synthon for the synthesis of a variety of carborane-functionalized molecules. Diels-Alder reaction of o-carboryne with furans gave a series of carborane-fused o...o-Carboryne （1,2-dehydro-o-carborane） is a very useful synthon for the synthesis of a variety of carborane-functionalized molecules. Diels-Alder reaction of o-carboryne with furans gave a series of carborane-fused oxanorbornenes in moderate to high yields using 1-OTf-1,2-C_2B_10H_11 as carboryne precursor. The resultant cycloadducts can undergo hydrogenation, cyclic oxidation, bromination, [4＋2]/[2＋2] cycloaddition and nucleophilic ring opening reaction to afford a variety of highly functionalized carboranes that may find applications as useful basic units in medicine and materials science.展开更多
of main observation and conclusion A palladium catalyzed oxidative annulation of 1-hydroxy-o-carborane with internal alkynes via regioselective B(3)—H bond activation has been developed for facile synthesis of a seri...of main observation and conclusion A palladium catalyzed oxidative annulation of 1-hydroxy-o-carborane with internal alkynes via regioselective B(3)—H bond activation has been developed for facile synthesis of a series of QB-substituted carborane-fused oxaboroles.These molecules can undergo intramolecular oxidative dehydrogenative coupling to afford carborane-fused large n systems for potential applications in organic materials.The reaction mechanism is also proposed,involving hydroxy deprotonation,nucleopalladation of alkyne,regioselective electrophilic B—H substitution and reductive eiiimination.展开更多
文摘o-Carboryne （1,2-dehydro-o-carborane） is a very useful synthon for the synthesis of a variety of carborane-functionalized molecules. Diels-Alder reaction of o-carboryne with furans gave a series of carborane-fused oxanorbornenes in moderate to high yields using 1-OTf-1,2-C_2B_10H_11 as carboryne precursor. The resultant cycloadducts can undergo hydrogenation, cyclic oxidation, bromination, [4＋2]/[2＋2] cycloaddition and nucleophilic ring opening reaction to afford a variety of highly functionalized carboranes that may find applications as useful basic units in medicine and materials science.
基金This work was supported by grants from the National NaturalScience Foundation of China(No.21772223)the Science andTechnology Commission ofShanghai Municipality(No.18590760800)the China Postdoctoral Science Foundation(No.BX20180341 to R.C.), the Shanghai Postdoctoral Excellence Program (No. 2018027 to R. C.), the Chinese Academy of Sciences,and Hong Kong Research Grants Council (No.14305017).
文摘of main observation and conclusion A palladium catalyzed oxidative annulation of 1-hydroxy-o-carborane with internal alkynes via regioselective B(3)—H bond activation has been developed for facile synthesis of a series of QB-substituted carborane-fused oxaboroles.These molecules can undergo intramolecular oxidative dehydrogenative coupling to afford carborane-fused large n systems for potential applications in organic materials.The reaction mechanism is also proposed,involving hydroxy deprotonation,nucleopalladation of alkyne,regioselective electrophilic B—H substitution and reductive eiiimination.
