Wereport a base-promoted catalyst-free protocol for the highly regioselective hydroacylation of styrenes with hydrazones derived from naturally abundant aldehydes.This protocolgeneratedlinearketoneswith goodfunctional...Wereport a base-promoted catalyst-free protocol for the highly regioselective hydroacylation of styrenes with hydrazones derived from naturally abundant aldehydes.This protocolgeneratedlinearketoneswith goodfunctional grouptolerance anda broadsubstrate scope under mild conditions.Mechanistic studies showed that the addition of hydrazone anion to a styrene double bond was the key step,different from previoushydroacylationpathways(viaorganometallic complexes or radical intermediates).展开更多
Isofunctional reactions involving the cleavage of carbon-carbon double bonds(C=C)hold an important position in organic synthesis,as they allow for the restructuring of alkene carbon chains and enable the exchange of f...Isofunctional reactions involving the cleavage of carbon-carbon double bonds(C=C)hold an important position in organic synthesis,as they allow for the restructuring of alkene carbon chains and enable the exchange of functional groups without introducing exogenous groups.Currently,these reactions are primarily divided into C=C/C=C metathesis and C=C/C=O metathesis,with most relying on the use of transition metal catalysts.We report herein a C=C/CH_(2) metathesis reaction that obviates the need for transition metals and directing groups,and is characterized by economic and straightforward operation.This reaction not only facilitates the replacement of nitriles with ketones,but also enables the replacement of ketones with nitriles,demonstrating great universality.展开更多
Coupling reactions between haloarenes and arenes(including heteroarenes)that are conducted without added transition metals but in the presence of KOtBu or NaOtBu,have been a topic of great interest since their discove...Coupling reactions between haloarenes and arenes(including heteroarenes)that are conducted without added transition metals but in the presence of KOtBu or NaOtBu,have been a topic of great interest since their discovery in 2008.Diverse organic structures act as additives that assist these reactions.These additives are converted into organic electron donors by the butoxide base and this leads to initiation of the coupling reactions,which proceed by radical chain mechanisms.This review provides an overview of the initiation stages of these reactions.展开更多
基金from the National Natural Science Foundation of China(grant no.21971093)the International Joint Research Centre for Green Catalysis and Synthesis(grant no.2016B01017),and the 111 project.
文摘Wereport a base-promoted catalyst-free protocol for the highly regioselective hydroacylation of styrenes with hydrazones derived from naturally abundant aldehydes.This protocolgeneratedlinearketoneswith goodfunctional grouptolerance anda broadsubstrate scope under mild conditions.Mechanistic studies showed that the addition of hydrazone anion to a styrene double bond was the key step,different from previoushydroacylationpathways(viaorganometallic complexes or radical intermediates).
基金supported by the National Natural Science Foundation of China(22071159)Sichuan Science and Technology Program(2018JY560)。
文摘Isofunctional reactions involving the cleavage of carbon-carbon double bonds(C=C)hold an important position in organic synthesis,as they allow for the restructuring of alkene carbon chains and enable the exchange of functional groups without introducing exogenous groups.Currently,these reactions are primarily divided into C=C/C=C metathesis and C=C/C=O metathesis,with most relying on the use of transition metal catalysts.We report herein a C=C/CH_(2) metathesis reaction that obviates the need for transition metals and directing groups,and is characterized by economic and straightforward operation.This reaction not only facilitates the replacement of nitriles with ketones,but also enables the replacement of ketones with nitriles,demonstrating great universality.
基金EPSRCGSKthe University of Strathclyde for funding(AJS)
文摘Coupling reactions between haloarenes and arenes(including heteroarenes)that are conducted without added transition metals but in the presence of KOtBu or NaOtBu,have been a topic of great interest since their discovery in 2008.Diverse organic structures act as additives that assist these reactions.These additives are converted into organic electron donors by the butoxide base and this leads to initiation of the coupling reactions,which proceed by radical chain mechanisms.This review provides an overview of the initiation stages of these reactions.
