Organic synthesis plays a central role in chemistry. The cre-ation of compounds with new properties and functions both distinguishes synthetic chemistry from other sciences and also emphasizes chemistry’s central pla...Organic synthesis plays a central role in chemistry. The cre-ation of compounds with new properties and functions both distinguishes synthetic chemistry from other sciences and also emphasizes chemistry’s central place in science. In principle, the possibilities for atomic and molecular manipulation are unlimited, which provides a firm molecular basis for biosci-ence, materials science and medical science. Man-made chemi-cals have entered many research fields where they play im-portant roles. Synthesis is changing all aspects of human socie-ty and improving the quality of our life. Catalysts are展开更多
α-Amino radicals are highly reactive and synthetically valuable species.However,their instability and short lifetime limit their applications in organic synthesis.This work has demonstrated a catalytic strategy for i...α-Amino radicals are highly reactive and synthetically valuable species.However,their instability and short lifetime limit their applications in organic synthesis.This work has demonstrated a catalytic strategy for in situ generation of persistentα-amino radicals from primary amines without protection of the NH2 group.In the presence of a carbonyl catalyst,primary amines could be converted into imines,which underwent deprotection and subsequent single electron transfer(SET)to produce resonancestabilizedα-imino radicals.The persistentα-imino radicals underwent cross-coupling with another carbon radical or addition towardπ-systems,enabling new and challenging transformations that were not readily achievable through ionic pathways.By employing this strategy,we achieved directα-cross-coupling of NH2-unprotected benzylamines and sterically hindered alkyl iodides with pyridoxal as the catalyst,producing a diverse array of bulkyα-branched benzyl alkylamines and cyclic amines in good yields.The reaction mechanism involved SET and radical/radical coupling processes,demonstrating the process of radical carbonyl catalysis for the first time.展开更多
A synergistic Pd/Zn dual chiral catalyst system has been developed for the stereodivergent transformation of Morita–Baylis–Hillman(MBH)carbonates and unprotectedα-hydroxyketones to afford the corresponding allylati...A synergistic Pd/Zn dual chiral catalyst system has been developed for the stereodivergent transformation of Morita–Baylis–Hillman(MBH)carbonates and unprotectedα-hydroxyketones to afford the corresponding allylation products(>50 examples).These products bearing vicinal stereocenters were obtained in high yields with excellent regio-/diastereo-/enantioselectivities.On cyclization in an acidic medium,the allylation products could transform to the corresponding acyl-functionalizedβ,γ-disubstitutedα-methylene-γ-butyrolactones(AMGBLs).All four stereoisomers of AMGBL were readily accessed using the same starting materials with full control of the stereochemistry of the contiguous stereogenic centers,simply by switching the chiral ligand combination for the Pd/Zn system.A nucleophilic site-divergent reactivity was observed for the allylation of primary and secondaryα-hydroxyketones,suggesting that distinct enolate intermediates might have prevailed in these reactions.展开更多
The dinuclear magnesium complexes generated in situ from the reaction of chiral multidentate semi-azacrown ether ligands with n-BuzMg were found to be efficient catalysts for enantioselective ring-opening of meso-epox...The dinuclear magnesium complexes generated in situ from the reaction of chiral multidentate semi-azacrown ether ligands with n-BuzMg were found to be efficient catalysts for enantioselective ring-opening of meso-epox- ides with aniline derivatives, affording the corresponding chiral β-amino alcohols in good yields with up to 90% ee.展开更多
The spiro concept for chiral ligand design represents an important contribution to the area of asymmetric catalysis. Due to the considerable difficulties in the construction of enantiopure all-carbon spiro backbones, ...The spiro concept for chiral ligand design represents an important contribution to the area of asymmetric catalysis. Due to the considerable difficulties in the construction of enantiopure all-carbon spiro backbones, the development of catalytic asymmetric synthesis of chiral spiro structures via short steps is highly valuable. Herein we present our studies on the catalytic asymmetric synthesis of aromatic spiroketals and the corresponding diphos- phine （SKP） ligands.展开更多
Oxazolones are structural subunits in numerous natural products and designed molecules with substantial pharmacological properties.Here,a palladium-catalyzed chemodivergent regio-and enantioselective allylic alkylatio...Oxazolones are structural subunits in numerous natural products and designed molecules with substantial pharmacological properties.Here,a palladium-catalyzed chemodivergent regio-and enantioselective allylic alkylation of 4-or 5-substituted oxazol-2(3H)-ones with Morita-Baylis-Hillman(MBH)adducts has been developed using a spiroketal-based diphosphine as the ligand(50 examples).Interestingly,4-substituted oxazol-2(3H)-ones acted as a C-nucleophiles in the reaction to afford a range of chiral 4,5-substituted oxazol-2(3H)-ones in high yields(72-99%)with good to excellent chemo-,regio-,and enantioselectivities(C/N 95:5->99:1,b/l 91:9->99:1,85-98%ee).When a N-nucleophile was used under otherwise identical conditions,5-substituted oxazol-2(3H)-ones delivered a range of chiral 3,5-substituted oxazol-2(3H)-ones in high yields(68-98%)with good regio-and enantioselectivities(b/l 71:29-91:9,66-94%ee).The synthesis can be readily performed on gram scale under fairly low catalyst loadings,and the utility of the protocol was showcased in the facile transformation of the products into more elaborate chiral molecules.展开更多
Enzymes are the core for biological transformations in nature.Their structures and functions have drawn enormous attention from biologists as well as chemists since last century.The large demand of bioactive molecules...Enzymes are the core for biological transformations in nature.Their structures and functions have drawn enormous attention from biologists as well as chemists since last century.The large demand of bioactive molecules and the pursuit of efficiency and greenness of synthesis have spurred the rapid development of biomimetic chemistry in the past several decades.Biomimetic asymmetric catalysis,mimicking the structures and functions of enzymes,has been recognized as one of the most promising synthetic strategies for the synthesis of valuable chiral compounds.This review summarizes the evolution of asymmetric catalysis inspired by aldolases,vitamin B_(1)/B_(6)-dependent enzymes,NAD(P)H,flavin,hydrogenases,heme oxygenases,nonheme oxygenases,and dinuclear/multinuclear metalloenzymes in aspects of biomimetic design,catalyst development and related catalytic transformations.Those well-established synthetic approaches originating from biological reactions have demonstrated the unique prowess of biomimetic asymmetric catalysis in bridging the gap between bio-catalysis and chemical synthesis.展开更多
Professor Chengye Yuan and Professor Li-Xin Dai,Members of Chinese Academy of Sciences,are eminent organic chemists in China.They have made significant contributions in the field of organic chemistry in the last 6 dec...Professor Chengye Yuan and Professor Li-Xin Dai,Members of Chinese Academy of Sciences,are eminent organic chemists in China.They have made significant contributions in the field of organic chemistry in the last 6 decades in China.Coincidentally,they were both born in 1924 and have worked at Shanghai Institute of Organic Chemistry(SIOC)as colleagues for about 60 years.We would like to take this wonderful occasion to organize this special issue of Chinese Journal of Chemistry to celebrate their 90th birthdays.展开更多
文摘Organic synthesis plays a central role in chemistry. The cre-ation of compounds with new properties and functions both distinguishes synthetic chemistry from other sciences and also emphasizes chemistry’s central place in science. In principle, the possibilities for atomic and molecular manipulation are unlimited, which provides a firm molecular basis for biosci-ence, materials science and medical science. Man-made chemi-cals have entered many research fields where they play im-portant roles. Synthesis is changing all aspects of human socie-ty and improving the quality of our life. Catalysts are
基金the generous financial support from the National Key R&D Program of China(grant no.2023YFA1506402)the National Natural Science Foundation of China(grant nos.22271192,22401189 and 22403065)+1 种基金Shanghai Municipal Science and Technology Major Project,Shanghai Engineering Research Center of Green Energy Chemical Engineering(grant no.18DZ2254200)China Postdoctoral Science Foundation(grant no.2024M752075).
文摘α-Amino radicals are highly reactive and synthetically valuable species.However,their instability and short lifetime limit their applications in organic synthesis.This work has demonstrated a catalytic strategy for in situ generation of persistentα-amino radicals from primary amines without protection of the NH2 group.In the presence of a carbonyl catalyst,primary amines could be converted into imines,which underwent deprotection and subsequent single electron transfer(SET)to produce resonancestabilizedα-imino radicals.The persistentα-imino radicals underwent cross-coupling with another carbon radical or addition towardπ-systems,enabling new and challenging transformations that were not readily achievable through ionic pathways.By employing this strategy,we achieved directα-cross-coupling of NH2-unprotected benzylamines and sterically hindered alkyl iodides with pyridoxal as the catalyst,producing a diverse array of bulkyα-branched benzyl alkylamines and cyclic amines in good yields.The reaction mechanism involved SET and radical/radical coupling processes,demonstrating the process of radical carbonyl catalysis for the first time.
基金the National Key R&D Program of China(grant nos.2023YFA1506700,2022YFA1503702,and 2021YFF0701602)National Natural Science Foundation of China(NSFC,grant nos.22231011 and 22271303)Shanghai Scientific and Technological Innovation Project,China(grant no.22JC1401000).
文摘A synergistic Pd/Zn dual chiral catalyst system has been developed for the stereodivergent transformation of Morita–Baylis–Hillman(MBH)carbonates and unprotectedα-hydroxyketones to afford the corresponding allylation products(>50 examples).These products bearing vicinal stereocenters were obtained in high yields with excellent regio-/diastereo-/enantioselectivities.On cyclization in an acidic medium,the allylation products could transform to the corresponding acyl-functionalizedβ,γ-disubstitutedα-methylene-γ-butyrolactones(AMGBLs).All four stereoisomers of AMGBL were readily accessed using the same starting materials with full control of the stereochemistry of the contiguous stereogenic centers,simply by switching the chiral ligand combination for the Pd/Zn system.A nucleophilic site-divergent reactivity was observed for the allylation of primary and secondaryα-hydroxyketones,suggesting that distinct enolate intermediates might have prevailed in these reactions.
文摘The dinuclear magnesium complexes generated in situ from the reaction of chiral multidentate semi-azacrown ether ligands with n-BuzMg were found to be efficient catalysts for enantioselective ring-opening of meso-epox- ides with aniline derivatives, affording the corresponding chiral β-amino alcohols in good yields with up to 90% ee.
文摘The spiro concept for chiral ligand design represents an important contribution to the area of asymmetric catalysis. Due to the considerable difficulties in the construction of enantiopure all-carbon spiro backbones, the development of catalytic asymmetric synthesis of chiral spiro structures via short steps is highly valuable. Herein we present our studies on the catalytic asymmetric synthesis of aromatic spiroketals and the corresponding diphos- phine （SKP） ligands.
基金financial supports from the National Key R&D Program of China(grant nos.2022YFA1503702 and 2021YFF0701602)NSFC(grant nos.22231011 and 22271303).
文摘Oxazolones are structural subunits in numerous natural products and designed molecules with substantial pharmacological properties.Here,a palladium-catalyzed chemodivergent regio-and enantioselective allylic alkylation of 4-or 5-substituted oxazol-2(3H)-ones with Morita-Baylis-Hillman(MBH)adducts has been developed using a spiroketal-based diphosphine as the ligand(50 examples).Interestingly,4-substituted oxazol-2(3H)-ones acted as a C-nucleophiles in the reaction to afford a range of chiral 4,5-substituted oxazol-2(3H)-ones in high yields(72-99%)with good to excellent chemo-,regio-,and enantioselectivities(C/N 95:5->99:1,b/l 91:9->99:1,85-98%ee).When a N-nucleophile was used under otherwise identical conditions,5-substituted oxazol-2(3H)-ones delivered a range of chiral 3,5-substituted oxazol-2(3H)-ones in high yields(68-98%)with good regio-and enantioselectivities(b/l 71:29-91:9,66-94%ee).The synthesis can be readily performed on gram scale under fairly low catalyst loadings,and the utility of the protocol was showcased in the facile transformation of the products into more elaborate chiral molecules.
基金supported by the National Natural Science Foundation of China(22231011,22221002,22031006,21831008,22271192,92256301,92256303,91956116)the NSFC Distinguished Young Scholars(22225107)the Major Program of the Lanzhou Institute of Chemical Physics,Chinese Academy of Sciences(ZYFZFX-9)。
文摘Enzymes are the core for biological transformations in nature.Their structures and functions have drawn enormous attention from biologists as well as chemists since last century.The large demand of bioactive molecules and the pursuit of efficiency and greenness of synthesis have spurred the rapid development of biomimetic chemistry in the past several decades.Biomimetic asymmetric catalysis,mimicking the structures and functions of enzymes,has been recognized as one of the most promising synthetic strategies for the synthesis of valuable chiral compounds.This review summarizes the evolution of asymmetric catalysis inspired by aldolases,vitamin B_(1)/B_(6)-dependent enzymes,NAD(P)H,flavin,hydrogenases,heme oxygenases,nonheme oxygenases,and dinuclear/multinuclear metalloenzymes in aspects of biomimetic design,catalyst development and related catalytic transformations.Those well-established synthetic approaches originating from biological reactions have demonstrated the unique prowess of biomimetic asymmetric catalysis in bridging the gap between bio-catalysis and chemical synthesis.
文摘Professor Chengye Yuan and Professor Li-Xin Dai,Members of Chinese Academy of Sciences,are eminent organic chemists in China.They have made significant contributions in the field of organic chemistry in the last 6 decades in China.Coincidentally,they were both born in 1924 and have worked at Shanghai Institute of Organic Chemistry(SIOC)as colleagues for about 60 years.We would like to take this wonderful occasion to organize this special issue of Chinese Journal of Chemistry to celebrate their 90th birthdays.
