The efficient construction of functionalized polycyclic structures is an imports nt objective in organic synthesis.Herein,we disclose a three-step"[2+n]"annulation method for the transformation of cyclic ket...The efficient construction of functionalized polycyclic structures is an imports nt objective in organic synthesis.Herein,we disclose a three-step"[2+n]"annulation method for the transformation of cyclic ketones to fused enimines and enones.The method relies on the Suzuki coupling reaction and the amide reductive alkenylation reaction.A series of fused bicyclic(6/6,6/7,8/7)and tricyclic(6/6/6;6/6/7,6/5/7)ring systems bearing an α,β-enimine or an α,β-enone functionality have been synthetized in good overall yields.展开更多
Enones are widely explored in synthetic chemistry as fundamental building blocks for a wide range of reactions and exhibit intriguing biological activities that are pivotal for drug discovery.The development of synthe...Enones are widely explored in synthetic chemistry as fundamental building blocks for a wide range of reactions and exhibit intriguing biological activities that are pivotal for drug discovery.The development of synthetic strategies for highly efficient preparation of enones thereby receives intense attention,in particular through the transition metal-catalyzed coupling reactions.Here,we describe a carbene-catalyzed cross dehydrogenative coupling(CDC)reaction that enables effective assembly of simple aldehydes and alkenes to afford a diverse set of enone derivatives.Mechanistically,the in situ generated aryl radical is pivotal to“activate”the alkene by forming an allyl radical through intermolecular hydrogen atom transfer(HAT)pathway and thus forging the carbon-carbon bond formation with aldehyde as the acyl synthon.Notably,our method represents the first example on the enone synthesis through coupling of“non-functionalized”aldehydes and alkenes as coupling partners,and offers a distinct organocatalytic pathway to the transition metal-catalyzed coupling transformations.展开更多
Comprehensive Summary Catalytic dehydrogenation,with its exceptional atom economy and chemoselectivity,offers a highly desirable yet challenging approach for converting multiple environmentally friendly alcohols into ...Comprehensive Summary Catalytic dehydrogenation,with its exceptional atom economy and chemoselectivity,offers a highly desirable yet challenging approach for converting multiple environmentally friendly alcohols into crucial molecules.Furthermore,the utilization of catalysts based on abundant elements found on Earth for alcohol dehydrogenation to produce acryl ketone holds significant promise as a versatile strategy in synthesizing key building blocks for numerous pharmaceutical applications.The present study describes a practical Co-catalyzed cascade dehydrogenative Claisen condensation of secondary alcohols with esters,facilitating the synthesis of a wide range of 3-hydroxy-prop-2-en-1-ones.We introduce a catalytic system based on novel and scalable indazole NNP-ligands coordinated to cobalt for efficient dehydrogenations of secondary alcohols,and propose a plausible reaction mechanism supported by control experiments and labeling studies.Notably,it allows for the streamlined synthesis of multiple pharmaceuticals in one-pot.展开更多
The nucleophilic addition of Ti(IV) enolate derived from methyl aryl ketones to α, β–unsaturated compounds was found to be highly selective to give 1, 2 addition products.
A series of novel chiral diphosphite ligands have been synthesized from（1R,2R）-trans-1,2-cyclohexanediol,（1S,2S）-trans-1,2-cyclohexanediol, racemic trans-1,2-cyclohexanediol and chlorophosphoric acid diary ester, ...A series of novel chiral diphosphite ligands have been synthesized from（1R,2R）-trans-1,2-cyclohexanediol,（1S,2S）-trans-1,2-cyclohexanediol, racemic trans-1,2-cyclohexanediol and chlorophosphoric acid diary ester, and were successfully employed in the Cu-catalyzed asymmetric 1,4-conjugate addition of diethylzinc to cyclohexenone with up to 99% ee. It was found that ligand 1,2-bis[（R）-1,10-binaphthyl-2,2＇-diyl]phosphitecyclohexanediol 6a derived from racemic diol skeleton can show similar catalytic performance compared with ligand（1R,2R）-bis[（R）-1,1＇-binaphthyl-2,2＇-diyl]phosphitecyclohexanediol 6a＇ derived from enantiopure starting material. A significant dependence of stereoselectivity on the type of enone and the ring size of the cyclic enone was observed. Moreover, the configuration of the products was mainly determined by the configuration of the binaphthyl moieties of diphosphite ligands in the 1,4-addition of cyclic enones.展开更多
Chiral sulfonamides derived from(d)-10-camphorsulfonyl chloride and chiral amines were prepared and used in the copper-catalyzed conjugate addition of organometallic reagents to enones.The chiral sulfonamides/CuCN cat...Chiral sulfonamides derived from(d)-10-camphorsulfonyl chloride and chiral amines were prepared and used in the copper-catalyzed conjugate addition of organometallic reagents to enones.The chiral sulfonamides/CuCN catalysts provided high catalytic activity and moderate enantioselectivity in the conjugate addition of diethylzinc to 2-cyclohexenone and 2-cyclohepteneone,but low enantioselectivity to the 2-cyclopentenone and acyclic enones.展开更多
A convergent approach to 1,5-hydroxy ketones,the general precursors for constructing the C ring of bryostatins,has been developed via a Zn/Cu-promoted conjugate addition of a-hydroxy iodides with enones.The reaction l...A convergent approach to 1,5-hydroxy ketones,the general precursors for constructing the C ring of bryostatins,has been developed via a Zn/Cu-promoted conjugate addition of a-hydroxy iodides with enones.The reaction leads to direct formation of the C21-C22 bond and tolerates diverse functionalities at the C17-,C18-and C24-positions.The approach also enables a more concise synthesis of the known C ring intermediate(10 longest linear steps and 14 total steps),in contrast to its previous synthesis(17 longest linear steps and 22 total steps) in our total synthesis of bryostatin 8.展开更多
Ni(0)-catalyzed regio-and diastereodivergent[4+2]annulation of biphenylenes withα,βunsaturated ketones is described.This solvent-controlled diastereodivergent reaction integrates C-C bond cleavage of biphenylene and...Ni(0)-catalyzed regio-and diastereodivergent[4+2]annulation of biphenylenes withα,βunsaturated ketones is described.This solvent-controlled diastereodivergent reaction integrates C-C bond cleavage of biphenylene and C=C double bond insertion selectivity,offering a mild approach to all possible diastereoisomers of 9,10-dihydrophenanthrene derivatives from the same starting materials.展开更多
A series of（Z）-2-chloro-1,3-diarylpropen-1-ones were unexpectedly synthesized in moderate yields by treatment of easily available 2,3-epoxy-1,3-diarylpropan-1-ones with Vilsmeier reagent,which was derived from bis（...A series of（Z）-2-chloro-1,3-diarylpropen-1-ones were unexpectedly synthesized in moderate yields by treatment of easily available 2,3-epoxy-1,3-diarylpropan-1-ones with Vilsmeier reagent,which was derived from bis（trichloromethyl） carbonate（BTC, triphosgene） and DMF.A possible mechanism was also proposed,where sequential ring-opening,halogenation and elimination reactions were involved.展开更多
A new facile, efficient and very mild entry to the synthesis of 3-（1H-indol-3-yl）-1, 3-diarylpropan-l-ones is presented. The procedure utilizes phosphotungstic acid （5 mol%） as a catalyst for the Michael addition ...A new facile, efficient and very mild entry to the synthesis of 3-（1H-indol-3-yl）-1, 3-diarylpropan-l-ones is presented. The procedure utilizes phosphotungstic acid （5 mol%） as a catalyst for the Michael addition of indole to α,β-unsaturated ketones in good yield in acetonitrile as solvent.展开更多
基金the National Natural Science Foundation of China(Nos.21672176 and 21332007)the National Key R&D Program of China(grant No.2017YFA0207302)the Program for Changjiang Scholars and Innovative Research Team in University(PCSIRT)of Ministry of Education.
文摘The efficient construction of functionalized polycyclic structures is an imports nt objective in organic synthesis.Herein,we disclose a three-step"[2+n]"annulation method for the transformation of cyclic ketones to fused enimines and enones.The method relies on the Suzuki coupling reaction and the amide reductive alkenylation reaction.A series of fused bicyclic(6/6,6/7,8/7)and tricyclic(6/6/6;6/6/7,6/5/7)ring systems bearing an α,β-enimine or an α,β-enone functionality have been synthetized in good overall yields.
基金funding supports from the National Natural Science Foundation of China(Nos.21732002,22061007,22071036,and 22207022)Frontiers Science Center for Asymmetric Synthesis and Medicinal Molecules,National Natural Science Fund for Excellent Young Scientists Fund Program(Overseas),the starting grant of Guizhou University[No.(2022)47)]+10 种基金Department of Education,Guizhou Province[Qianjiaohe KY No.(2020)004]The 10 Talent Plan(Shicengci)of Guizhou Province(No.[2016]5649)Science and Technology Department of Guizhou Province(Nos.[Qiankehe-jichu-ZK[2022]zhongdian024],[2018]2802,[2019]1020,QKHJC-ZK[2022]-455)Department of Education of Guizhou Province(No.QJJ(2022)205)Program of Introducing Talents of Discipline to Universities of China(111 Program,No.D20023)at Guizhou UniversitySingapore National Research Foundation under its NRF Investigatorship(No.NRF-NRFI2016–06)Competitive Research Program(No.NRF-CRP22–2019–0002)Ministry of Education,Singapore,under its MOE Ac RF Tier 1 Award(Nos.RG7/20,RG70/21)MOE AcRF Tier 2(No.MOE2019-T2–2–117)MOE AcRF Tier 3 Award(No.MOE2018-T3–1–003)a Chair Professorship Grant,and Nanyang Technological University。
文摘Enones are widely explored in synthetic chemistry as fundamental building blocks for a wide range of reactions and exhibit intriguing biological activities that are pivotal for drug discovery.The development of synthetic strategies for highly efficient preparation of enones thereby receives intense attention,in particular through the transition metal-catalyzed coupling reactions.Here,we describe a carbene-catalyzed cross dehydrogenative coupling(CDC)reaction that enables effective assembly of simple aldehydes and alkenes to afford a diverse set of enone derivatives.Mechanistically,the in situ generated aryl radical is pivotal to“activate”the alkene by forming an allyl radical through intermolecular hydrogen atom transfer(HAT)pathway and thus forging the carbon-carbon bond formation with aldehyde as the acyl synthon.Notably,our method represents the first example on the enone synthesis through coupling of“non-functionalized”aldehydes and alkenes as coupling partners,and offers a distinct organocatalytic pathway to the transition metal-catalyzed coupling transformations.
基金supported by the National Natural Science Foundation of China(22002067,22202228)the Fund Program for the Scientific Activities of Selected Returned Overseas Professionals in Shanxi Province(20220052)the Science and Technology Project of Shanxi Province(202103021223457,202303021221256)and Research Project Supported by Shanxi Scholarship Council of China.
文摘Comprehensive Summary Catalytic dehydrogenation,with its exceptional atom economy and chemoselectivity,offers a highly desirable yet challenging approach for converting multiple environmentally friendly alcohols into crucial molecules.Furthermore,the utilization of catalysts based on abundant elements found on Earth for alcohol dehydrogenation to produce acryl ketone holds significant promise as a versatile strategy in synthesizing key building blocks for numerous pharmaceutical applications.The present study describes a practical Co-catalyzed cascade dehydrogenative Claisen condensation of secondary alcohols with esters,facilitating the synthesis of a wide range of 3-hydroxy-prop-2-en-1-ones.We introduce a catalytic system based on novel and scalable indazole NNP-ligands coordinated to cobalt for efficient dehydrogenations of secondary alcohols,and propose a plausible reaction mechanism supported by control experiments and labeling studies.Notably,it allows for the streamlined synthesis of multiple pharmaceuticals in one-pot.
文摘The nucleophilic addition of Ti(IV) enolate derived from methyl aryl ketones to α, β–unsaturated compounds was found to be highly selective to give 1, 2 addition products.
基金the National Natural Science Foundation of China (Nos. 20773147, 21073211, and 21174155)
文摘A series of novel chiral diphosphite ligands have been synthesized from（1R,2R）-trans-1,2-cyclohexanediol,（1S,2S）-trans-1,2-cyclohexanediol, racemic trans-1,2-cyclohexanediol and chlorophosphoric acid diary ester, and were successfully employed in the Cu-catalyzed asymmetric 1,4-conjugate addition of diethylzinc to cyclohexenone with up to 99% ee. It was found that ligand 1,2-bis[（R）-1,10-binaphthyl-2,2＇-diyl]phosphitecyclohexanediol 6a derived from racemic diol skeleton can show similar catalytic performance compared with ligand（1R,2R）-bis[（R）-1,1＇-binaphthyl-2,2＇-diyl]phosphitecyclohexanediol 6a＇ derived from enantiopure starting material. A significant dependence of stereoselectivity on the type of enone and the ring size of the cyclic enone was observed. Moreover, the configuration of the products was mainly determined by the configuration of the binaphthyl moieties of diphosphite ligands in the 1,4-addition of cyclic enones.
文摘Chiral sulfonamides derived from(d)-10-camphorsulfonyl chloride and chiral amines were prepared and used in the copper-catalyzed conjugate addition of organometallic reagents to enones.The chiral sulfonamides/CuCN catalysts provided high catalytic activity and moderate enantioselectivity in the conjugate addition of diethylzinc to 2-cyclohexenone and 2-cyclohepteneone,but low enantioselectivity to the 2-cyclopentenone and acyclic enones.
基金the financial support from the National Natural Science Foundation of China(No.21921002)the NationalScience and Technology Major Project of the Ministry of Science and Technology of the People’s Republic of China(No.2018ZX09711001-005-004)the Fundamental Research Funds for the Central Universities(No.2012017yjsy210)。
文摘A convergent approach to 1,5-hydroxy ketones,the general precursors for constructing the C ring of bryostatins,has been developed via a Zn/Cu-promoted conjugate addition of a-hydroxy iodides with enones.The reaction leads to direct formation of the C21-C22 bond and tolerates diverse functionalities at the C17-,C18-and C24-positions.The approach also enables a more concise synthesis of the known C ring intermediate(10 longest linear steps and 14 total steps),in contrast to its previous synthesis(17 longest linear steps and 22 total steps) in our total synthesis of bryostatin 8.
基金supported by the National Natural Science Foundation of China (Nos. 21801067, U1804283, 21801066)the Central Plains Scholars and Scientists Studio Fund (No. 2018002)+2 种基金the Project funded by the Natural Science Foundation of Henan (Nos. 202300410225, 212300410181, 222102310562 and 201901023)China Postdoctoral Science Foundation (Nos. 2020T130176 and 2020M682306)financial support from Henan Key Laboratory of Organic Functional Molecules and Drug Innovation
文摘Ni(0)-catalyzed regio-and diastereodivergent[4+2]annulation of biphenylenes withα,βunsaturated ketones is described.This solvent-controlled diastereodivergent reaction integrates C-C bond cleavage of biphenylene and C=C double bond insertion selectivity,offering a mild approach to all possible diastereoisomers of 9,10-dihydrophenanthrene derivatives from the same starting materials.
基金the National Natural Science Foundation of China(Nos.20806073 and 20876147)the National Key Technology Research and Development Program(No.2007BAI34B06) for financial support
文摘A series of（Z）-2-chloro-1,3-diarylpropen-1-ones were unexpectedly synthesized in moderate yields by treatment of easily available 2,3-epoxy-1,3-diarylpropan-1-ones with Vilsmeier reagent,which was derived from bis（trichloromethyl） carbonate（BTC, triphosgene） and DMF.A possible mechanism was also proposed,where sequential ring-opening,halogenation and elimination reactions were involved.
文摘A new facile, efficient and very mild entry to the synthesis of 3-（1H-indol-3-yl）-1, 3-diarylpropan-l-ones is presented. The procedure utilizes phosphotungstic acid （5 mol%） as a catalyst for the Michael addition of indole to α,β-unsaturated ketones in good yield in acetonitrile as solvent.
