A Zn/NH4Cl system was exploited at room temperature to promote the Michael addition reaction of various primary and secondary amines with α,β-unsaturated esters,nitriles,amides,and ketones to give the corresponding ...A Zn/NH4Cl system was exploited at room temperature to promote the Michael addition reaction of various primary and secondary amines with α,β-unsaturated esters,nitriles,amides,and ketones to give the corresponding saturated amines under the mild condition in high yield.展开更多
Chiral activated alkene, L-menthyl acrylate and (+)-N-α-phenylethyl acrylamide, induced asymmetric Baylis-HiUman reaction of aromatic aldehydes was realized at 25℃ for 7 days in Me3N/H2O/solvent homogeneous mediu...Chiral activated alkene, L-menthyl acrylate and (+)-N-α-phenylethyl acrylamide, induced asymmetric Baylis-HiUman reaction of aromatic aldehydes was realized at 25℃ for 7 days in Me3N/H2O/solvent homogeneous medium. The corresponding Baylis-Hillman adducts were obtained in good chemical yield with moderate to excellent diastereoselectivity (up to 99% de).展开更多
The mechanism is investigated for Cp^(tBu)Rh(OH)_(2)-catalyzed annulation of 2-biphenylboronic acid with three activated alkenes using M06-2X functional.The reaction comprises transmetalation via two steps and followi...The mechanism is investigated for Cp^(tBu)Rh(OH)_(2)-catalyzed annulation of 2-biphenylboronic acid with three activated alkenes using M06-2X functional.The reaction comprises transmetalation via two steps and following C-H activation producing reactive Rh-biphenyl complex with two Rh—Cσbonds.After the coordination/insertion of alkenes,respective fused or bridged cyclic products are yielded depending on different alkenes accompanied by the release of CptBuRh.The promotion of Cp^(tBu)Rh(OH)_(2) lies in the barrier decrease of transmetalation and C-H activation ready for coordination/insertion ensuring the smooth progress of common rate-limiting reductive elimination.The stereoselective transfer and ring rotation are specific for benzoquinone and cyclopropenone.The role of Rh(III)catalyst and release of Rh(I)is supported by Multiwfn analysis on frontier molecular orbital(FMO)of specific transiton states(TSs)and Mayer bond order(MBO)value of vital bonding,breaking.展开更多
Comprehensive Summary The simultaneous construction of two vicinal C—C bonds in a molecule remains a significant challenge.In this work,we disclose an electroreductive carboarylation of activated alkenes under mild,t...Comprehensive Summary The simultaneous construction of two vicinal C—C bonds in a molecule remains a significant challenge.In this work,we disclose an electroreductive carboarylation of activated alkenes under mild,transition metal-free conditions.Utilizing readily available starting materials(electron-deficient aryl bromides,activated alkenes,and CO_(2)),this method demonstrates broad substrate scope and good functional group tolerance.Notably,this strategy enables the addition of two distinct electrophiles across an alkene in a highly chemo-and regioselective manner.展开更多
An expeditious and effective method for synthesis of isoxazoline from aldoximes and activated alkenes using cetyltrimethylammonium cerium nitrate at room temperature is described.Reaction was completed within short ti...An expeditious and effective method for synthesis of isoxazoline from aldoximes and activated alkenes using cetyltrimethylammonium cerium nitrate at room temperature is described.Reaction was completed within short time period in high yields at room temperature.展开更多
A novel Ag-mediated dialkylation reaction of alkenes was disclosed,in which AgF was essential to activate C-H bond of acetonitrile.This reaction provided an efficient way to nitrile-containing spirooxindoles from read...A novel Ag-mediated dialkylation reaction of alkenes was disclosed,in which AgF was essential to activate C-H bond of acetonitrile.This reaction provided an efficient way to nitrile-containing spirooxindoles from readily available(1H-indol-3-yl)methanamine derivatives.展开更多
基金Supported by the Scientific Research Foundation for the Returned Overseas Chinese Scholars,Ministry of Education,China
文摘A Zn/NH4Cl system was exploited at room temperature to promote the Michael addition reaction of various primary and secondary amines with α,β-unsaturated esters,nitriles,amides,and ketones to give the corresponding saturated amines under the mild condition in high yield.
基金the National Natural Science Foundation of China(20472033)the Ph.D.Programs of Ministry of Education of China(No.20020055002)for generous financial support for our programs.
文摘Chiral activated alkene, L-menthyl acrylate and (+)-N-α-phenylethyl acrylamide, induced asymmetric Baylis-HiUman reaction of aromatic aldehydes was realized at 25℃ for 7 days in Me3N/H2O/solvent homogeneous medium. The corresponding Baylis-Hillman adducts were obtained in good chemical yield with moderate to excellent diastereoselectivity (up to 99% de).
基金National Natural Science Foundation of China(Nos.21973056,21972079)Natural Science Foundation of Shandong Province,China(No.ZR2019MB050)Project of the Key Laboratory of Agricultural Film Application of Ministry of Agriculture and Rural Affairs,China.
文摘The mechanism is investigated for Cp^(tBu)Rh(OH)_(2)-catalyzed annulation of 2-biphenylboronic acid with three activated alkenes using M06-2X functional.The reaction comprises transmetalation via two steps and following C-H activation producing reactive Rh-biphenyl complex with two Rh—Cσbonds.After the coordination/insertion of alkenes,respective fused or bridged cyclic products are yielded depending on different alkenes accompanied by the release of CptBuRh.The promotion of Cp^(tBu)Rh(OH)_(2) lies in the barrier decrease of transmetalation and C-H activation ready for coordination/insertion ensuring the smooth progress of common rate-limiting reductive elimination.The stereoselective transfer and ring rotation are specific for benzoquinone and cyclopropenone.The role of Rh(III)catalyst and release of Rh(I)is supported by Multiwfn analysis on frontier molecular orbital(FMO)of specific transiton states(TSs)and Mayer bond order(MBO)value of vital bonding,breaking.
基金supported by the National Key R&D Program of China(2022YFA1505100,2021YFA1500104)National Natural Science Foundation of China(22031008,22201222)+1 种基金Science Foundation of Wuhan(2023020201020266,2020010601012192)Jiangxi Normal University Doctoral Research Initiation Fund Project(12017081,12022796).
文摘Comprehensive Summary The simultaneous construction of two vicinal C—C bonds in a molecule remains a significant challenge.In this work,we disclose an electroreductive carboarylation of activated alkenes under mild,transition metal-free conditions.Utilizing readily available starting materials(electron-deficient aryl bromides,activated alkenes,and CO_(2)),this method demonstrates broad substrate scope and good functional group tolerance.Notably,this strategy enables the addition of two distinct electrophiles across an alkene in a highly chemo-and regioselective manner.
文摘An expeditious and effective method for synthesis of isoxazoline from aldoximes and activated alkenes using cetyltrimethylammonium cerium nitrate at room temperature is described.Reaction was completed within short time period in high yields at room temperature.
基金We are grateful for financial support from 973 Program(No.2011CB808700)NSFC(Nos.21225210,20923005 and 21121062)+1 种基金STCSM(No.11JC1415000)the CAS/SAFEA International Partnership Program for Creative Research Teams.
文摘A novel Ag-mediated dialkylation reaction of alkenes was disclosed,in which AgF was essential to activate C-H bond of acetonitrile.This reaction provided an efficient way to nitrile-containing spirooxindoles from readily available(1H-indol-3-yl)methanamine derivatives.