Reduction of prochiral ferrocenyl ketones 2a-e in the presence of 10 mol% of chiral beta -amino alcohols 4a-b provides 1-ferrocenyl alcohols 1a-e in high yields (> 85%) with high optically purity (e.e. up to 96%).
Using chiral hydrogenesterification reaction as the key step, the stereoselective synthesisof (+)-nuciferal 1, (+)-(E)-nuciferol 2 and (+)-α-curcumene 3 has been achieved.
A series of α-amino acids are obtained in 72-96% optical yields by alkylation of the ketimine derived from(+)-2-hydroxy-pinan-3-one and(-)-menthyl glycinate fol- lowed by hydrolysis of the alkylated intermediates wit...A series of α-amino acids are obtained in 72-96% optical yields by alkylation of the ketimine derived from(+)-2-hydroxy-pinan-3-one and(-)-menthyl glycinate fol- lowed by hydrolysis of the alkylated intermediates with mineral acid.The double asymmetric induction are explained by the transition model of lithium enolate.展开更多
Inherently chiral 6,7-diphenyldibenzo[e,g][1,4]diazocine(DDD)has been synthesized enantioselectively for the first time via chiral phosphoric acid(CPA)-catalyzed cyclocondensation of readily available[1,1′-biphenyl]-...Inherently chiral 6,7-diphenyldibenzo[e,g][1,4]diazocine(DDD)has been synthesized enantioselectively for the first time via chiral phosphoric acid(CPA)-catalyzed cyclocondensation of readily available[1,1′-biphenyl]-2,2′-diamine(1a)and benzil(2a)in 82%yield,with 98%ee under mild reaction conditions.The strategy could also be applied to racemic biaryl diamines through kinetic resolution.The unexpectedly high interconversion energy barriers between the enantiomers(ΔG=39.5 kcal/mol)and the chemical stability rendered DDD an ideal platform for developing new chiral ligands and catalysts.Unique inherently chiralDDD-based phosphoramidites,phosphoric acid,mono-and diphosphine ligands were prepared from optically pure diphenol derivative DDDOL as a common precursor.Preliminary asymmetric reactions catalyzed by Pd or Rh in the presence of newly developed ligands exhibited comparable or even better enantioselectivities than the corresponding BINOLor SPINOL-derived ligands.Density functional theory calculation revealed the origin of the enantioselectivity during the process.展开更多
Optically active terminal 1,2-diols were prepared with high enantiopurity via the TMS-quinidine-catalyzed en- antioselective cyclization of acyl chlorides and oxaziridine, followed by reductive ring-opening of the cyc...Optically active terminal 1,2-diols were prepared with high enantiopurity via the TMS-quinidine-catalyzed en- antioselective cyclization of acyl chlorides and oxaziridine, followed by reductive ring-opening of the cycloadducts.展开更多
The Cp;Rh(Ⅲ)-catalyzed asymmetric cascade C-H coupling/intramolecular cyclization of azomethine imines with propargyl carbonates has been developed, affording a variety of chiral tetracyclic indenopyrazolopyrazolone ...The Cp;Rh(Ⅲ)-catalyzed asymmetric cascade C-H coupling/intramolecular cyclization of azomethine imines with propargyl carbonates has been developed, affording a variety of chiral tetracyclic indenopyrazolopyrazolone frameworks with good substrate/functional group tolerance and enantioselectivity(up to 97:3 er). Combined experimental studies and DFT calculations revealed the Rh(Ⅲ)-catalyzed stepwise annulation process and clarified the synergy coordination mode of dual directing groups in tuning the selectivity.展开更多
Studies on the synthesis of antifungal and anticancer natural product,pseudolaric acid B,have led to the enantioselective synthesis of di-epi-trans-fused[5-7]-bicyclic co re skeleton.The synthesis was achieved in 10 l...Studies on the synthesis of antifungal and anticancer natural product,pseudolaric acid B,have led to the enantioselective synthesis of di-epi-trans-fused[5-7]-bicyclic co re skeleton.The synthesis was achieved in 10 linear steps,which features the Sharpless asymmetric epoxidation,cyanide-opening reaction of epoxide,and intramolecular[5+2]cycloaddition reaction as the key transformations.The stereochemistry was determined by the X-ray crystallographic analysis.展开更多
(4S,5S)-and(4S,5R)-5-Hydroxy-4-decanolide(1a and 1b),the proposed autoregula- tors from Strepotomyces Griseus were synthesized from a propargyl alcohol 2 in an overall yield of 30%,employing the Sharpless asymmetric e...(4S,5S)-and(4S,5R)-5-Hydroxy-4-decanolide(1a and 1b),the proposed autoregula- tors from Strepotomyces Griseus were synthesized from a propargyl alcohol 2 in an overall yield of 30%,employing the Sharpless asymmetric epoxidation as the key step.展开更多
A simplified procedure for enantioselective synthesis of (S)-(+)-2-(6-methoxyl-2- naphthyl) propionic acid ((S)-(+)-naproxen), starting from (6-methoxy-a-naphthyl) -1-propanone, with D-mannitol as auxiliary catalyzed ...A simplified procedure for enantioselective synthesis of (S)-(+)-2-(6-methoxyl-2- naphthyl) propionic acid ((S)-(+)-naproxen), starting from (6-methoxy-a-naphthyl) -1-propanone, with D-mannitol as auxiliary catalyzed by SmCl3 in onepot is described. The yield is 87.5 %(ee value 99 %).展开更多
The title complex, (1S)-1,1'-bis{[N-ethyl-N-(1-methylethyl)-amino]carbonyl}-2- (hydroxyldiphenylmethyl)-ferrocene ([Fe(C24H22NO2)(C11H16NO)]2·H2O, Mr = 1207.13), was synthesized via (-)-Sparteine-m...The title complex, (1S)-1,1'-bis{[N-ethyl-N-(1-methylethyl)-amino]carbonyl}-2- (hydroxyldiphenylmethyl)-ferrocene ([Fe(C24H22NO2)(C11H16NO)]2·H2O, Mr = 1207.13), was synthesized via (-)-Sparteine-mediated enantioselective directed ortho-lithiation of 1,1‘-bis{[N- ethyl-N-(1-methylethyl)-amino]carbonyl}-2-(hydroxydiphenylmethyl)-ferrocene. The structure of the rifle compound was determined by X-ray single-crystal diffraction. The crystal belongs to the orthorhombic system, space group P212121, with a = 10.266(2), b = 17.676(4), c = 34.097(7)A, V = 6187(2)A3, Z = 4, C70H86Fe2N4O7, Dc = 1.296 g/cm^3,μ = 0.527 mm^-1, T= 113(2) K, F(000) = 2568, the final R = 0.0469 and wR = 0.0984 for 13940 observed reflections with I 〉 2σ(I). The neighboring ferrocene derivatives are joined into dimers via O-H…O=C intermolecular hydrogen bonding by a water molecule. Besides, the dimers form neat rows along the a axis.展开更多
Main observation and conclusion A highly enantioselective 2,3-allenylation of acyclic and cyclicα-imino carboxylates via a synergistic bimetallic Pd/Cu catalysis with the same commercially available(R,Rp)-iPr-FOXAP(a...Main observation and conclusion A highly enantioselective 2,3-allenylation of acyclic and cyclicα-imino carboxylates via a synergistic bimetallic Pd/Cu catalysis with the same commercially available(R,Rp)-iPr-FOXAP(also as Phosferrox,(R,R)-[2-(4’-i-propyloxazolin-2’-yl)ferrocenyl]diphenyl phosphine)ligand for both metals affording optically active 2,3-butadienylα-amino acid derivatives in high to excellent yields with excellent enantioselectivities has been developed.展开更多
A chiron approach-based enantioselective synthesis of designed tricyclic tyrosine analogue D-2 was developed. A SmI2-mediated free radical cyclization, an intramolecular Friedel-Crafts reaction and an intramolecular M...A chiron approach-based enantioselective synthesis of designed tricyclic tyrosine analogue D-2 was developed. A SmI2-mediated free radical cyclization, an intramolecular Friedel-Crafts reaction and an intramolecular Mannich reaction served as key steps. These key steps were optimized and repeated in good yields. All the stereochemistries in the synthesis were established and confirmed.展开更多
The enantioselective total synthesis of representative members of the eburnamine-vincamine alkaloids(+)-vincamine,(-)-eburnamonine,and(-)-criocerine has been accomplished.The synthesis took advantage of a highly stere...The enantioselective total synthesis of representative members of the eburnamine-vincamine alkaloids(+)-vincamine,(-)-eburnamonine,and(-)-criocerine has been accomplished.The synthesis took advantage of a highly stereoselective Ir-catalyzed hydrogenation/lactamization cascade reaction,which allows for the stereo-selective construction of the C/D rings as well as the installation of the critical cis-C20/C21 relative stereo-chemistry of the eburnamine-vincamine alkaloid skeleton in one pot.展开更多
文摘Reduction of prochiral ferrocenyl ketones 2a-e in the presence of 10 mol% of chiral beta -amino alcohols 4a-b provides 1-ferrocenyl alcohols 1a-e in high yields (> 85%) with high optically purity (e.e. up to 96%).
文摘Using chiral hydrogenesterification reaction as the key step, the stereoselective synthesisof (+)-nuciferal 1, (+)-(E)-nuciferol 2 and (+)-α-curcumene 3 has been achieved.
基金This work was supported by the National Natural Science Foundation of China
文摘A series of α-amino acids are obtained in 72-96% optical yields by alkylation of the ketimine derived from(+)-2-hydroxy-pinan-3-one and(-)-menthyl glycinate fol- lowed by hydrolysis of the alkylated intermediates with mineral acid.The double asymmetric induction are explained by the transition model of lithium enolate.
基金the National Natural Science Foundation of China(grant nos.21871268 and 22071250)the Natural Science Foundation of Guangdong Province of China(grant no.2020A1515011428)the“BAGUI Scholar”Program of Guangxi Province of China,and the SKLRD Project(grant no.SKLRD-Z-202014)for financial support.
文摘Inherently chiral 6,7-diphenyldibenzo[e,g][1,4]diazocine(DDD)has been synthesized enantioselectively for the first time via chiral phosphoric acid(CPA)-catalyzed cyclocondensation of readily available[1,1′-biphenyl]-2,2′-diamine(1a)and benzil(2a)in 82%yield,with 98%ee under mild reaction conditions.The strategy could also be applied to racemic biaryl diamines through kinetic resolution.The unexpectedly high interconversion energy barriers between the enantiomers(ΔG=39.5 kcal/mol)and the chemical stability rendered DDD an ideal platform for developing new chiral ligands and catalysts.Unique inherently chiralDDD-based phosphoramidites,phosphoric acid,mono-and diphosphine ligands were prepared from optically pure diphenol derivative DDDOL as a common precursor.Preliminary asymmetric reactions catalyzed by Pd or Rh in the presence of newly developed ligands exhibited comparable or even better enantioselectivities than the corresponding BINOLor SPINOL-derived ligands.Density functional theory calculation revealed the origin of the enantioselectivity during the process.
基金Acknowledgement This work was supported by the National Natural Science Foundation of China (No. 21072195) and the Major State Basic Research Development Program (No. 2011CB808600).
文摘Optically active terminal 1,2-diols were prepared with high enantiopurity via the TMS-quinidine-catalyzed en- antioselective cyclization of acyl chlorides and oxaziridine, followed by reductive ring-opening of the cycloadducts.
基金National Natural Science Foundation of China (NSFC,Nos.21877020,22007020)Guangdong Natural Science Funds for Distinguished Young Scholar (No.2017A030306031)Natural Science Foundation of Guangdong Province (No.2019A1515010935) for financial support on this study。
文摘The Cp;Rh(Ⅲ)-catalyzed asymmetric cascade C-H coupling/intramolecular cyclization of azomethine imines with propargyl carbonates has been developed, affording a variety of chiral tetracyclic indenopyrazolopyrazolone frameworks with good substrate/functional group tolerance and enantioselectivity(up to 97:3 er). Combined experimental studies and DFT calculations revealed the Rh(Ⅲ)-catalyzed stepwise annulation process and clarified the synergy coordination mode of dual directing groups in tuning the selectivity.
基金the financial support from the National Natural Science Foundation of China(Nos.21302078,21572089,21732001,21672017)the Program for Changjiang Scholars and the Innovative Research Team in Universities(PCSIRT:No.IRT_15R28)+3 种基金the State Key Basic Research Program of the PRC(No.2018YFC0310900)Shenzhen Science and Technology Innovation Committee(No.JCYJ20180504165454447)Shenzhen Basic Research Program(No.20180202)the National Ten Thousand Talent Program(the Leading Talent Tier)。
文摘Studies on the synthesis of antifungal and anticancer natural product,pseudolaric acid B,have led to the enantioselective synthesis of di-epi-trans-fused[5-7]-bicyclic co re skeleton.The synthesis was achieved in 10 linear steps,which features the Sharpless asymmetric epoxidation,cyanide-opening reaction of epoxide,and intramolecular[5+2]cycloaddition reaction as the key transformations.The stereochemistry was determined by the X-ray crystallographic analysis.
文摘(4S,5S)-and(4S,5R)-5-Hydroxy-4-decanolide(1a and 1b),the proposed autoregula- tors from Strepotomyces Griseus were synthesized from a propargyl alcohol 2 in an overall yield of 30%,employing the Sharpless asymmetric epoxidation as the key step.
文摘A simplified procedure for enantioselective synthesis of (S)-(+)-2-(6-methoxyl-2- naphthyl) propionic acid ((S)-(+)-naproxen), starting from (6-methoxy-a-naphthyl) -1-propanone, with D-mannitol as auxiliary catalyzed by SmCl3 in onepot is described. The yield is 87.5 %(ee value 99 %).
基金supported by the Major Program of National Natural Science Foundation of China (200572009)Beijing Natural Science Foundation Program and Scientific Research Key Program of Beijing Municipal Commission of Education (KZ200610011006)
文摘The title complex, (1S)-1,1'-bis{[N-ethyl-N-(1-methylethyl)-amino]carbonyl}-2- (hydroxyldiphenylmethyl)-ferrocene ([Fe(C24H22NO2)(C11H16NO)]2·H2O, Mr = 1207.13), was synthesized via (-)-Sparteine-mediated enantioselective directed ortho-lithiation of 1,1‘-bis{[N- ethyl-N-(1-methylethyl)-amino]carbonyl}-2-(hydroxydiphenylmethyl)-ferrocene. The structure of the rifle compound was determined by X-ray single-crystal diffraction. The crystal belongs to the orthorhombic system, space group P212121, with a = 10.266(2), b = 17.676(4), c = 34.097(7)A, V = 6187(2)A3, Z = 4, C70H86Fe2N4O7, Dc = 1.296 g/cm^3,μ = 0.527 mm^-1, T= 113(2) K, F(000) = 2568, the final R = 0.0469 and wR = 0.0984 for 13940 observed reflections with I 〉 2σ(I). The neighboring ferrocene derivatives are joined into dimers via O-H…O=C intermolecular hydrogen bonding by a water molecule. Besides, the dimers form neat rows along the a axis.
基金Financial support from the National Natural Science Foundation of China(Grant No.21690063 to S.M.,and Grant No.21901158 to X.H.)is greatly appreciated.We thank Mr.Huanan Wang in this group for reproducing the results of(R)-3'd,(Rm-3and(R)-17k,presented in Tables 2,3,and 4,respectively.
文摘Main observation and conclusion A highly enantioselective 2,3-allenylation of acyclic and cyclicα-imino carboxylates via a synergistic bimetallic Pd/Cu catalysis with the same commercially available(R,Rp)-iPr-FOXAP(also as Phosferrox,(R,R)-[2-(4’-i-propyloxazolin-2’-yl)ferrocenyl]diphenyl phosphine)ligand for both metals affording optically active 2,3-butadienylα-amino acid derivatives in high to excellent yields with excellent enantioselectivities has been developed.
基金the Major State Basic Research Development Program (No. G2000077500), the National Natural Science Foundation of China (No. 20321202), and Chinese Academy of Sciences and Shanghai Municipal Commission of Science and Technology.
文摘A chiron approach-based enantioselective synthesis of designed tricyclic tyrosine analogue D-2 was developed. A SmI2-mediated free radical cyclization, an intramolecular Friedel-Crafts reaction and an intramolecular Mannich reaction served as key steps. These key steps were optimized and repeated in good yields. All the stereochemistries in the synthesis were established and confirmed.
基金support from the National Natural Science Foundation of China(No.U21A20278)the Sichuan Science and Technology Program(No.2021YJ0221).
文摘The enantioselective total synthesis of representative members of the eburnamine-vincamine alkaloids(+)-vincamine,(-)-eburnamonine,and(-)-criocerine has been accomplished.The synthesis took advantage of a highly stereoselective Ir-catalyzed hydrogenation/lactamization cascade reaction,which allows for the stereo-selective construction of the C/D rings as well as the installation of the critical cis-C20/C21 relative stereo-chemistry of the eburnamine-vincamine alkaloid skeleton in one pot.