A regiodivergent hydrophosphorylation of enynes with phosphites has been developed using earthabundant nickel catalyst.The manipulation of regioselectivity can be achieved by regulating the insertion order of alkyne b...A regiodivergent hydrophosphorylation of enynes with phosphites has been developed using earthabundant nickel catalyst.The manipulation of regioselectivity can be achieved by regulating the insertion order of alkyne bonds with(RO)_(2)P(O)-Ni-H or R_(2)P(O)O-Ni-H species,respectively.Under the Ni/Xantphos catalysis,4,1-hydrophosphorylation is selectively obtained while the adding of acid can promote reactions towards 1,2-addition.By employing an additional Pd-H catalysis,2,1-hydrophosphorylation is also an accessible task in one-pot reaction.Mechanistic studies and analysis have also been performed to interpret the origin of the regioselective regulation.This work highlights the arts in accessing different regioisomers by diverting common elementary reaction steps.展开更多
Aliphatic C(sp^(3))-H moieties are ubiquitous in numerous organic compounds.Direct functionalization of inert C(sp^(3))-H bonds is a powerful and straightforward approach for the efficient construction of diverse carb...Aliphatic C(sp^(3))-H moieties are ubiquitous in numerous organic compounds.Direct functionalization of inert C(sp^(3))-H bonds is a powerful and straightforward approach for the efficient construction of diverse carbon-carbon or carbon-heteroatom bonds.Chelating group directed metal-catalyzed remote functionalization of readily available alkenes has emerged as an appealing strategy for rapidly accessing various value-added aliphatic molecules.With the aid of directing groups,variousα-,β-andγ-functionalized alkanes could be synthesized smoothly with excellent regioselectivity.The preferred formation of a stable five-or six-membered metallacycle intermediate terminates the chain-walking at a specific methylene site,which serves as the driving force for excellent site-selective migratory functionalization.This review herein is aimed at summarizing the recent progress on the metal-catalyzed regiodivergent functionalization of unactivated alkenes by merging alkene isomerization and cross-coupling with the assistance of directing auxiliary.Last but not least,the current situations and future directions in this field are highlighted and discussed.展开更多
Chain-walking has emerged as a promising strategy in organic synthetic methodology,but achieving site-selectivity in reactions involving competition among multiple potential positions remains a challenge.In this study...Chain-walking has emerged as a promising strategy in organic synthetic methodology,but achieving site-selectivity in reactions involving competition among multiple potential positions remains a challenge.In this study,we presented a novel approach to ligand-modulated,nickel-catalyzed regiodivergent alkenylboration of allylarenes.Our method allows for highly chemoselective preparation of two classes of structurally different alkenyl boronates from the same starting by simply switching the ligand.Mechanistic investigations involving experiments and calculations suggest that the ligand-modulating regiodivergence arises from either regioselectiveβ-H elimination or oxidative addition with organic halides.Our findings offer valuable insight into addressing site-selective issues in chain-walking reactions with multiple thermodynamically stable factors.展开更多
Regiodivergent 1,2-hydroboration of 1,3-dienes with pinacolborane has been accomplished by well-defined cobalt complexes of different bidentate ligands. The iminopyridine-cobalt system is selective for Markovnikov 1,2...Regiodivergent 1,2-hydroboration of 1,3-dienes with pinacolborane has been accomplished by well-defined cobalt complexes of different bidentate ligands. The iminopyridine-cobalt system is selective for Markovnikov 1,2-hydroboration to form allylboronates, while the FOXAP-cobalt(FOXAP=(S)-1-(diphenylphosphino)-2-[(S)-4-isopropyloxazolin-2-yl]ferrocene) catalyst effects the complementary anti-Markonikv 1,2-hydroboration to afford homoallyboronates with high regioselectivity.展开更多
A nickel-hydride(Ni H)-catalyzed migratory and nonmigratory hydroalkylation reaction of 2-alkenyl azaarenes with alkyl iodines has been established through strategic modulation of N-or P-donor ligands.This method enab...A nickel-hydride(Ni H)-catalyzed migratory and nonmigratory hydroalkylation reaction of 2-alkenyl azaarenes with alkyl iodines has been established through strategic modulation of N-or P-donor ligands.This method enables the synthesis of diverseβ-orγ-branched aromatic N-heterocycles.The mild regiodivergent protocols exhibit wide substrate scope,excellent functional tolerance,and great reaction yield with remarkable regioselectivity.Importantly,deuterium labeling studies reveal Ni H-catalyzed interrupted chain-walking mode as the mechanism behind remotedβ-selective hydroalkylation reaction—an interesting phenomenon mediated through aromatic imine directing groups.展开更多
Regiodivergent asymmetric cycloadditions from the same set of starting materials offer interesting opportunities for rapid construction of optically active cyclic molecules with structural diversity.However,this remai...Regiodivergent asymmetric cycloadditions from the same set of starting materials offer interesting opportunities for rapid construction of optically active cyclic molecules with structural diversity.However,this remains a challenging task due to the difficulty of simultaneously controlling the regio-,diastereo-,and enantioselectivity in the ring formation processes.To address this long-standing problem.展开更多
Herein,we disclose a ligand-controlled,directing group-assisted strategy to facilitate NiH-catalyzed hydroalkynylation of allyl amides at remoteα-position adjacent to nitrogen and initial olefinic site in a predictab...Herein,we disclose a ligand-controlled,directing group-assisted strategy to facilitate NiH-catalyzed hydroalkynylation of allyl amides at remoteα-position adjacent to nitrogen and initial olefinic site in a predictable and switchable manner.Bromoalkynedependent regiodivergent hydroalkynylation and asymmetric hydroalkynylation with a wide alkyne scope were achieved,producingα-and(enantioenriched)β-branched alkynyl-functionalized amine derivatives from the same raw materials.The formation of a carbonyl-ligated 5-or 6-membered nickelacycle intermediate via Ni migration or nonmigration was believed to be the key step in controlling the regioselectivity.This asymmetric protocol could be applied to synthesizing other value-added chiral aliphatic amines.展开更多
基金Financial support from Dalian Outstanding Young Scientific Talent(No.2020RJ05)the National Natural Science Foundation of China(Nos.22071239,21971234)。
文摘A regiodivergent hydrophosphorylation of enynes with phosphites has been developed using earthabundant nickel catalyst.The manipulation of regioselectivity can be achieved by regulating the insertion order of alkyne bonds with(RO)_(2)P(O)-Ni-H or R_(2)P(O)O-Ni-H species,respectively.Under the Ni/Xantphos catalysis,4,1-hydrophosphorylation is selectively obtained while the adding of acid can promote reactions towards 1,2-addition.By employing an additional Pd-H catalysis,2,1-hydrophosphorylation is also an accessible task in one-pot reaction.Mechanistic studies and analysis have also been performed to interpret the origin of the regioselective regulation.This work highlights the arts in accessing different regioisomers by diverting common elementary reaction steps.
基金the National Natural Science Foundation of China(No.22001116)the Basic and Applied Basic Research Foundation of Guangdong Province(No.2020A1515110816)funds provided by Changzhou University(No.ZMF23020217)。
文摘Aliphatic C(sp^(3))-H moieties are ubiquitous in numerous organic compounds.Direct functionalization of inert C(sp^(3))-H bonds is a powerful and straightforward approach for the efficient construction of diverse carbon-carbon or carbon-heteroatom bonds.Chelating group directed metal-catalyzed remote functionalization of readily available alkenes has emerged as an appealing strategy for rapidly accessing various value-added aliphatic molecules.With the aid of directing groups,variousα-,β-andγ-functionalized alkanes could be synthesized smoothly with excellent regioselectivity.The preferred formation of a stable five-or six-membered metallacycle intermediate terminates the chain-walking at a specific methylene site,which serves as the driving force for excellent site-selective migratory functionalization.This review herein is aimed at summarizing the recent progress on the metal-catalyzed regiodivergent functionalization of unactivated alkenes by merging alkene isomerization and cross-coupling with the assistance of directing auxiliary.Last but not least,the current situations and future directions in this field are highlighted and discussed.
基金support are from the National Natural Science Foundation of China(22122107)the Fundamental Research Funds for Central Universities(2042021kf0190).
文摘Chain-walking has emerged as a promising strategy in organic synthetic methodology,but achieving site-selectivity in reactions involving competition among multiple potential positions remains a challenge.In this study,we presented a novel approach to ligand-modulated,nickel-catalyzed regiodivergent alkenylboration of allylarenes.Our method allows for highly chemoselective preparation of two classes of structurally different alkenyl boronates from the same starting by simply switching the ligand.Mechanistic investigations involving experiments and calculations suggest that the ligand-modulating regiodivergence arises from either regioselectiveβ-H elimination or oxidative addition with organic halides.Our findings offer valuable insight into addressing site-selective issues in chain-walking reactions with multiple thermodynamically stable factors.
基金supported by the National Key R&D Program of China (2016YFA0202900, 2015CB856600)the National Natural Science Foundation of China (21825109, 21432011, 21572255, 21732006)+1 种基金Chinese Academy of Sciences (XDB20000000, QYZDB-SSWSLH016)Science and Technology Commission Shanghai Municipality (17JC1401200)
文摘Regiodivergent 1,2-hydroboration of 1,3-dienes with pinacolborane has been accomplished by well-defined cobalt complexes of different bidentate ligands. The iminopyridine-cobalt system is selective for Markovnikov 1,2-hydroboration to form allylboronates, while the FOXAP-cobalt(FOXAP=(S)-1-(diphenylphosphino)-2-[(S)-4-isopropyloxazolin-2-yl]ferrocene) catalyst effects the complementary anti-Markonikv 1,2-hydroboration to afford homoallyboronates with high regioselectivity.
基金supported by the Dalian Institute of Chemical Physics,the Chinese Academy of Sciencesthe National Natural Science Foundation of China(21472186,21272231)。
文摘A nickel-hydride(Ni H)-catalyzed migratory and nonmigratory hydroalkylation reaction of 2-alkenyl azaarenes with alkyl iodines has been established through strategic modulation of N-or P-donor ligands.This method enables the synthesis of diverseβ-orγ-branched aromatic N-heterocycles.The mild regiodivergent protocols exhibit wide substrate scope,excellent functional tolerance,and great reaction yield with remarkable regioselectivity.Importantly,deuterium labeling studies reveal Ni H-catalyzed interrupted chain-walking mode as the mechanism behind remotedβ-selective hydroalkylation reaction—an interesting phenomenon mediated through aromatic imine directing groups.
基金from the National Natural Science Foundation of China(grant nos.22071209 and 22071206)the National Youth Talent Support Program,the Natural Science Foundation of Fujian Province of China(grant no.2017J06006)+1 种基金the Fundamental Research Funds for the Central Universities(grant no.20720190048)Basic Disciplines Training Program for Top-notch Students of the Ministry of Education.
文摘Regiodivergent asymmetric cycloadditions from the same set of starting materials offer interesting opportunities for rapid construction of optically active cyclic molecules with structural diversity.However,this remains a challenging task due to the difficulty of simultaneously controlling the regio-,diastereo-,and enantioselectivity in the ring formation processes.To address this long-standing problem.
基金supported by the National Natural Science Foundation of China(grant no.21901185)funds provided by Tianjin Normal University,China.
文摘Herein,we disclose a ligand-controlled,directing group-assisted strategy to facilitate NiH-catalyzed hydroalkynylation of allyl amides at remoteα-position adjacent to nitrogen and initial olefinic site in a predictable and switchable manner.Bromoalkynedependent regiodivergent hydroalkynylation and asymmetric hydroalkynylation with a wide alkyne scope were achieved,producingα-and(enantioenriched)β-branched alkynyl-functionalized amine derivatives from the same raw materials.The formation of a carbonyl-ligated 5-or 6-membered nickelacycle intermediate via Ni migration or nonmigration was believed to be the key step in controlling the regioselectivity.This asymmetric protocol could be applied to synthesizing other value-added chiral aliphatic amines.
