of main observation and conclusion Oxygen atom transfer reactions between alkynes and heteroarene N-oxides are currently mediated by transition metal,such as gold,ruthenium or rhodium,but they have never been catalyze...of main observation and conclusion Oxygen atom transfer reactions between alkynes and heteroarene N-oxides are currently mediated by transition metal,such as gold,ruthenium or rhodium,but they have never been catalyzed by osmium.Herein,we report stepwise oxidations of terminal alkynes mediated by an osmium carbolong complex,using pyridine N-oxide as the oxidant,yielding novel aldehyde-or carboxylic acid-coordinated osmapentalyne derivatives selectively.The mechanism was illustrated by density functional theory calculations,providing a new route for oxygen atom transfer between heteroarene N-oxides and alkynes.展开更多
The reaction of a cyclic osmacarbyne complex with sodium azide led to the formation of a ring expansion-annulation product,a unique tetrazole annulated polycyclic metallacycle.The reaction proceeds by insertion of a n...The reaction of a cyclic osmacarbyne complex with sodium azide led to the formation of a ring expansion-annulation product,a unique tetrazole annulated polycyclic metallacycle.The reaction proceeds by insertion of a nitrogen atom into the metal carbon triple bond and the second azide participating in the[2+3]cycloaddition.The successful isolation and characterization of metalla-azirine complex and metallapyridinium derivative strongly validated the mechanism for the formation of the title complex.The work demonstrates a new strategy to enrich the varieties of aza-metallacyclic species.展开更多
基金We gratefully acknowledge the Guangdong Provincial Key Laboratory of Catalysis(No.2020B121201002)NSFC(Nos.U1705254 and 21931002)for their financial support.
文摘of main observation and conclusion Oxygen atom transfer reactions between alkynes and heteroarene N-oxides are currently mediated by transition metal,such as gold,ruthenium or rhodium,but they have never been catalyzed by osmium.Herein,we report stepwise oxidations of terminal alkynes mediated by an osmium carbolong complex,using pyridine N-oxide as the oxidant,yielding novel aldehyde-or carboxylic acid-coordinated osmapentalyne derivatives selectively.The mechanism was illustrated by density functional theory calculations,providing a new route for oxygen atom transfer between heteroarene N-oxides and alkynes.
基金This research was supported by the National Natural Science Foundation of China(Nos.22071206,U1705254,21931002)the Natural Science Foundation of Fujian Province of China(No.2020J01025).
文摘The reaction of a cyclic osmacarbyne complex with sodium azide led to the formation of a ring expansion-annulation product,a unique tetrazole annulated polycyclic metallacycle.The reaction proceeds by insertion of a nitrogen atom into the metal carbon triple bond and the second azide participating in the[2+3]cycloaddition.The successful isolation and characterization of metalla-azirine complex and metallapyridinium derivative strongly validated the mechanism for the formation of the title complex.The work demonstrates a new strategy to enrich the varieties of aza-metallacyclic species.
