Alkynes are versatile synthons in organic synthesis,as well as important structural moieties in bioactive molecules.Recently,transition metal-catalyzed hydroalkynylation of alkenes has been developed with reactive alk...Alkynes are versatile synthons in organic synthesis,as well as important structural moieties in bioactive molecules.Recently,transition metal-catalyzed hydroalkynylation of alkenes has been developed with reactive alkenes and alkenes bearing directing groups.However,the regioselective hydroalkynylation of simple alkenes is still challenging.Herein,we have developed a palladium-catalyzed Markovnikov hydroalkynylation of unactivated terminal alkenes,which provides an efficient approach for the synthesis of branched alkynyl compounds under mild conditions.This reaction features excellent functional group tolerance,good reaction yields and excellent regioselectivity.Moreover,the asymmetric hydroalkynylation reaction has also been achieved with moderate enantioselectivity by introducing a sterically bulky chiral Pyox ligand.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
Herein,an unprecedented nickel-catalyzed regioselective hydroalkynylation of unsymmetrical internal alkynes was realized with steric hindered resistance selectivity via the cyano-directing group strategy.Significantly...Herein,an unprecedented nickel-catalyzed regioselective hydroalkynylation of unsymmetrical internal alkynes was realized with steric hindered resistance selectivity via the cyano-directing group strategy.Significantly,the resulting 1,3-enyne products could be effectively employed in the synthesis of novel nitrogen-containing tricyclics compounds,that provided the potential candidate compound 8a(IC_(50)=2.6—6.1μmol/L)for the anti-tumor cell proliferation activity.Therefore,this work not only improves the transition-metal-catalyzed hydroalkynylation strategy of internal alkynes,but also exhibits versatility of 1,3-enynes in the construction of the complex bioactive chemical space.展开更多
基金the National Key R&D Program of China(No.2021YFA1500100)the National Nature Science Foundation of China(Nos.22101295,21971255,91956202,92256301 and 21821002)+1 种基金the Science and Technology Commission of Shanghai Municipality(Nos.20JC1417000 and 21520780100)the Youth Innovation Promotion Association,CAS(Y2022074).
文摘Alkynes are versatile synthons in organic synthesis,as well as important structural moieties in bioactive molecules.Recently,transition metal-catalyzed hydroalkynylation of alkenes has been developed with reactive alkenes and alkenes bearing directing groups.However,the regioselective hydroalkynylation of simple alkenes is still challenging.Herein,we have developed a palladium-catalyzed Markovnikov hydroalkynylation of unactivated terminal alkenes,which provides an efficient approach for the synthesis of branched alkynyl compounds under mild conditions.This reaction features excellent functional group tolerance,good reaction yields and excellent regioselectivity.Moreover,the asymmetric hydroalkynylation reaction has also been achieved with moderate enantioselectivity by introducing a sterically bulky chiral Pyox ligand.
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.
基金supported by the National Natural Science Foundation of China(22361003,82260676)Talent Project of Jiangxi Province(jxsq2019101065)+2 种基金the Jiangxi Provincial Natural Science Foundation(20224BAB216005,20232BAB216131)the Science and Technology Projects of Ganzhou(202101094462,2023PNS26854)The Start-up Fund of Gannan Medical University.
文摘Herein,an unprecedented nickel-catalyzed regioselective hydroalkynylation of unsymmetrical internal alkynes was realized with steric hindered resistance selectivity via the cyano-directing group strategy.Significantly,the resulting 1,3-enyne products could be effectively employed in the synthesis of novel nitrogen-containing tricyclics compounds,that provided the potential candidate compound 8a(IC_(50)=2.6—6.1μmol/L)for the anti-tumor cell proliferation activity.Therefore,this work not only improves the transition-metal-catalyzed hydroalkynylation strategy of internal alkynes,but also exhibits versatility of 1,3-enynes in the construction of the complex bioactive chemical space.
