We herein describe an enantio-and diastereoselective rhodium(I)-catalyzed defluorinative arylation of pentafluoroethyl alkenes with arylboronic acids.A new class of previously inaccessible functionalized fluoroalkenes...We herein describe an enantio-and diastereoselective rhodium(I)-catalyzed defluorinative arylation of pentafluoroethyl alkenes with arylboronic acids.A new class of previously inaccessible functionalized fluoroalkenes featuring a sp^(2)-carbon connected to F and CF_(3) can be synthesized.Using both 1,1-and 1,2-disubstituted alkene substrates,tetra-and trisubstituted fluoroalkene products are obtained in excellent Z/E selectivities with well-defined alkene geometry.These fluoroalkenes are potential synthons for accessing chiral compounds containing a stereogenic centre with F and CF_(3) group.展开更多
Planar organofluorine compounds are highly sought-after structural motifs.Herein,we present an enantioselective strategy for the synthesis of planar chiral fluoroalkenes via kinetic resolution of gem-difluorovinylferr...Planar organofluorine compounds are highly sought-after structural motifs.Herein,we present an enantioselective strategy for the synthesis of planar chiral fluoroalkenes via kinetic resolution of gem-difluorovinylferrocenes by copper-catalyzed hydrodefluorination in the presence of a base and diboron.This method was successfully applied to provide a diverse range of planar chiral gem-difluoroalkenes and Z-monofluoroalkenes with excellent regio-,stereo-and enantioselectivity.The resulting enantioenriched planar chiral fluoroalkenes could undergo various enantioretaining transformations,broadening their synthetic utility.Furthermore,density functional theory(DFT)calculations provide mechanistic insights into the origin of enantioselectivity,enhancing the understanding of this transformation.展开更多
Herein,we report a base-promoted,silylborane-mediated strategy for the transformation of fluorinated carbenes derived from fluoroalkyl ketones,enabling the efficient and stereoselective synthesis of diverse fluorinate...Herein,we report a base-promoted,silylborane-mediated strategy for the transformation of fluorinated carbenes derived from fluoroalkyl ketones,enabling the efficient and stereoselective synthesis of diverse fluorinated 1,3-dienes and alkenes.This metal-free protocol exhibits broad functional group tolerance,accommodating halogens,heteroarenes,and various perfluoroalkyl groups,providing streamlined access to fluorinated frameworks that are otherwise challenging to obtain using conventional methods.Mechanistic studies support a silyl radical-initiated pathway,wherein t-BuONa promotes the in-situ generation of silyl radicals that abstract allylic C–H bonds,triggering downstream selective defluorination.This work establishes a practical platform for the synthesis of valuable fluorinated building blocks and offers insights into silyl radical-driven transformations under metal-free conditions.展开更多
基金supported by the Research Grants Council of Hong Kong(CUHK 14301324 and JLFS/P-404/24)The Chinese University of Hong Kong(Strategic Seed Funding for Collaborative Research Scheme SSFCRS 2024-25).
文摘We herein describe an enantio-and diastereoselective rhodium(I)-catalyzed defluorinative arylation of pentafluoroethyl alkenes with arylboronic acids.A new class of previously inaccessible functionalized fluoroalkenes featuring a sp^(2)-carbon connected to F and CF_(3) can be synthesized.Using both 1,1-and 1,2-disubstituted alkene substrates,tetra-and trisubstituted fluoroalkene products are obtained in excellent Z/E selectivities with well-defined alkene geometry.These fluoroalkenes are potential synthons for accessing chiral compounds containing a stereogenic centre with F and CF_(3) group.
基金supported by the NSFC(No.22471063)the Natural Science Foundation of Henan Province(242300421351,252300421719)+1 种基金Education Department of Henan Province Natural Science Research Program(23A150037)Henan Postdoctoral Science Foundation(202103087)。
文摘Planar organofluorine compounds are highly sought-after structural motifs.Herein,we present an enantioselective strategy for the synthesis of planar chiral fluoroalkenes via kinetic resolution of gem-difluorovinylferrocenes by copper-catalyzed hydrodefluorination in the presence of a base and diboron.This method was successfully applied to provide a diverse range of planar chiral gem-difluoroalkenes and Z-monofluoroalkenes with excellent regio-,stereo-and enantioselectivity.The resulting enantioenriched planar chiral fluoroalkenes could undergo various enantioretaining transformations,broadening their synthetic utility.Furthermore,density functional theory(DFT)calculations provide mechanistic insights into the origin of enantioselectivity,enhancing the understanding of this transformation.
基金the Affiliated Hospital of North Sichuan Medical College(No.2022JB001)National Natural Science Foundation of China(No.22271031)+1 种基金the Science and Technology Department of Guizhou Province(No.QKHPTRC-[2019]009)Medical Imaging Key Laboratory of Sichuan Province(No.MiKL202401).
文摘Herein,we report a base-promoted,silylborane-mediated strategy for the transformation of fluorinated carbenes derived from fluoroalkyl ketones,enabling the efficient and stereoselective synthesis of diverse fluorinated 1,3-dienes and alkenes.This metal-free protocol exhibits broad functional group tolerance,accommodating halogens,heteroarenes,and various perfluoroalkyl groups,providing streamlined access to fluorinated frameworks that are otherwise challenging to obtain using conventional methods.Mechanistic studies support a silyl radical-initiated pathway,wherein t-BuONa promotes the in-situ generation of silyl radicals that abstract allylic C–H bonds,triggering downstream selective defluorination.This work establishes a practical platform for the synthesis of valuable fluorinated building blocks and offers insights into silyl radical-driven transformations under metal-free conditions.
