Transition metal-catalyzed allylic substitution is a key reaction for forming carbon-carbon and carbon-heteroatom bonds,with broad applications in organic synthesis.While most methods rely on“soft”stabilized nucleop...Transition metal-catalyzed allylic substitution is a key reaction for forming carbon-carbon and carbon-heteroatom bonds,with broad applications in organic synthesis.While most methods rely on“soft”stabilized nucleophiles,the use of“hard”unstabilized derivatives has been less explored due to their high reactivity and challenges associated with controlling regio-and stereoselectivity.This review highlights advances in catalytic allylic substitution with unstabilized organometallic nucleophiles,focusing on aryl,alkyl,allyl,alkenyl,alkynyl,benzyl,and allenyl reagents and their direct cross-coupling with acyclic and cyclic allylic substrates.Key developments are categorized by reaction type,including achiral,racemic,stereoselective,and stereospecific processes.These advancements provide deeper insight into the reaction progress,challenges,and limitations.We anticipate a better understanding of the underlying mechanistic intricacies will further broaden their applicability in target-directed synthesis.展开更多
Glycosides are essential structural motifs present in an array of important medicines,materials,and natural products[1].Nevertheless,the chemo-and stereoselective construction of the glycosidic linkage is a long-stand...Glycosides are essential structural motifs present in an array of important medicines,materials,and natural products[1].Nevertheless,the chemo-and stereoselective construction of the glycosidic linkage is a long-standing challenge because relatively minor variations in the glycosyl donor or acceptor’s structure can impact stereoselectivity,thus influencing the product's functional properties.展开更多
基金supported by the Natural Sciences and Engineering Research Council of Canada(NSERC)through a Discovery Grant and a Tier 1 Canada Research Chair(P.A.E)the Huxiang High-Level Talent Gathering Project from the Science and Technology Department of Hunan Province(2020RC5001)。
文摘Transition metal-catalyzed allylic substitution is a key reaction for forming carbon-carbon and carbon-heteroatom bonds,with broad applications in organic synthesis.While most methods rely on“soft”stabilized nucleophiles,the use of“hard”unstabilized derivatives has been less explored due to their high reactivity and challenges associated with controlling regio-and stereoselectivity.This review highlights advances in catalytic allylic substitution with unstabilized organometallic nucleophiles,focusing on aryl,alkyl,allyl,alkenyl,alkynyl,benzyl,and allenyl reagents and their direct cross-coupling with acyclic and cyclic allylic substrates.Key developments are categorized by reaction type,including achiral,racemic,stereoselective,and stereospecific processes.These advancements provide deeper insight into the reaction progress,challenges,and limitations.We anticipate a better understanding of the underlying mechanistic intricacies will further broaden their applicability in target-directed synthesis.
文摘Glycosides are essential structural motifs present in an array of important medicines,materials,and natural products[1].Nevertheless,the chemo-and stereoselective construction of the glycosidic linkage is a long-standing challenge because relatively minor variations in the glycosyl donor or acceptor’s structure can impact stereoselectivity,thus influencing the product's functional properties.
