A simple and efficient methodology for Markovnikov addition of azoles with vinyl acetate catalyzed by potassium tert-butoxide is described.N-heterocyclic compounds are synthesized from simple and commercially availabl...A simple and efficient methodology for Markovnikov addition of azoles with vinyl acetate catalyzed by potassium tert-butoxide is described.N-heterocyclic compounds are synthesized from simple and commercially available starting materials under mild conditions in high yields.展开更多
The reaction of[Co(PMe_(3))_(4)](1)with a redox-active NNN pincer ligand(L_(1))led us to isolate a unique binuclear cobalt complex([(PMe_(3))_(2)Co^(II)(L_(1)^(3−))CoI(PMe_(3))_(3)](2))anchored by a three-electron red...The reaction of[Co(PMe_(3))_(4)](1)with a redox-active NNN pincer ligand(L_(1))led us to isolate a unique binuclear cobalt complex([(PMe_(3))_(2)Co^(II)(L_(1)^(3−))CoI(PMe_(3))_(3)](2))anchored by a three-electron reduced L_(1)in its unusual coordination mode.Such an unprecedented binuclear pincer/allyl cobalt complex consisting of the mixed-valence oxidation state of cobalt ions(+1 and+2)is confirmed by various analytical techniques(XPS,EPR,and UV–vis),and the experimentally determined electronic structure is well corroborated by detailed theoretical studies based on DFT calculations.展开更多
Anti-Markovnikov hydroazidation of unactivated alkenes using ABX–N3 as an initiator has been developed at room temperature,wherein hydrogen azide(HN3)acts as both hydrogen and azidating agent.Notably,the HN3 reagent ...Anti-Markovnikov hydroazidation of unactivated alkenes using ABX–N3 as an initiator has been developed at room temperature,wherein hydrogen azide(HN3)acts as both hydrogen and azidating agent.Notably,the HN3 reagent was generated from azidotrimethylsilane(TMSN3)and acetic acid in situ.The reaction itself displays broad substrate scope,good yields and excellent regioselectivities.展开更多
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
We present a simple and straightforward protocol for hydrochlorination of terminal arylalkynes to vinyl chlorides using hydrogen chloride under mild reaction conditions. This protocol does not involve any metal cataly...We present a simple and straightforward protocol for hydrochlorination of terminal arylalkynes to vinyl chlorides using hydrogen chloride under mild reaction conditions. This protocol does not involve any metal catalysts or additives. It is simple, inexpensive, and easy to prepare, and exhibits good reaction activity. The hydrochlorination proceeds smoothly to yield unique regioselective products via the Markovnikov addition rule.展开更多
文摘A simple and efficient methodology for Markovnikov addition of azoles with vinyl acetate catalyzed by potassium tert-butoxide is described.N-heterocyclic compounds are synthesized from simple and commercially available starting materials under mild conditions in high yields.
基金the funding agencies SERB(CRG/2019/004185 and SPR/2019/001145)CSIR(01(2933)/18/EMR-II),and IIT Bombay for their financial support+1 种基金GR would like to thank DST and SERB(CRG/2018/00430,DST/CSA-03/2018-10SB/SJF/2019-20/12)for funding.PK would like to thank CSIR,DAAD and SERB for funding.AS would like to thank CSIR.PK and AS also thank the Department of Chemistry,IIT Bombay,for the instrumentation and server facilities.
文摘The reaction of[Co(PMe_(3))_(4)](1)with a redox-active NNN pincer ligand(L_(1))led us to isolate a unique binuclear cobalt complex([(PMe_(3))_(2)Co^(II)(L_(1)^(3−))CoI(PMe_(3))_(3)](2))anchored by a three-electron reduced L_(1)in its unusual coordination mode.Such an unprecedented binuclear pincer/allyl cobalt complex consisting of the mixed-valence oxidation state of cobalt ions(+1 and+2)is confirmed by various analytical techniques(XPS,EPR,and UV–vis),and the experimentally determined electronic structure is well corroborated by detailed theoretical studies based on DFT calculations.
基金supported by the National Basic Research Program of China(973-2015CB856600)the National Natural Science Foundation of China(21532009,21821002,21790330,21761142010)+2 种基金the Science and Technology Commission of Shanghai Municipality(17XD1404500,17QA1405200,17JC1401200)the strategic Priority Research Program(XDB20000000)the Key Research Program of Frontier Science(QYZDJSSW-SLH055)of the Chinese Academy of Sciences
文摘Anti-Markovnikov hydroazidation of unactivated alkenes using ABX–N3 as an initiator has been developed at room temperature,wherein hydrogen azide(HN3)acts as both hydrogen and azidating agent.Notably,the HN3 reagent was generated from azidotrimethylsilane(TMSN3)and acetic acid in situ.The reaction itself displays broad substrate scope,good yields and excellent regioselectivities.
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financial support from the National Basic Research Program of China(973 Program,No.2012CB720300)the Applied Basic Research Program of Bingtuan(No.2015AG001)the High-level Talent Scientific Research Project of Shihezi University(No.RCZX201405)
文摘We present a simple and straightforward protocol for hydrochlorination of terminal arylalkynes to vinyl chlorides using hydrogen chloride under mild reaction conditions. This protocol does not involve any metal catalysts or additives. It is simple, inexpensive, and easy to prepare, and exhibits good reaction activity. The hydrochlorination proceeds smoothly to yield unique regioselective products via the Markovnikov addition rule.
基金supported by the 973 Program of China(No.2009CB825300)the National Natural Science Foundation of China(Nos.20972175,20923005)the Science and Technology Commission of the Shanghai Municipality(No.11JC1415000)~~
