The stereoselective synthesis of 2 -chloro-4- substituted-phenyl-5, 5-dimthyl- 1,3, 2-dioxaphsphorinan- 2 - (thi) ones is described. only single trans-isomers were obtained when 1-substituted-phenyl-2, 2 -dimethyl-1,3...The stereoselective synthesis of 2 -chloro-4- substituted-phenyl-5, 5-dimthyl- 1,3, 2-dioxaphsphorinan- 2 - (thi) ones is described. only single trans-isomers were obtained when 1-substituted-phenyl-2, 2 -dimethyl-1,3 -propanediols (1) reacted with POCl3. But the stereoselectivity of cyclization reaction between (1) and PSCl3, depended greatly upon the reaction condition. The configurational assignments and the ratio of cis-/trans-diastereoisomers of the products were performed on the basis of 1 HNMR, 31PNMR and IR spectra and confirmed by X-ray diffraction展开更多
1-(4-hydroxy-3-methoxyphenyl)-2-(4-formyl-2-methoxyphenoxy)-propane-1,3-diol, A 8-O-4’ neolignan, has been stereoselectively synthesized in eight steps from ferulic acid, and the directly cis opening of epoxide in ep...1-(4-hydroxy-3-methoxyphenyl)-2-(4-formyl-2-methoxyphenoxy)-propane-1,3-diol, A 8-O-4’ neolignan, has been stereoselectively synthesized in eight steps from ferulic acid, and the directly cis opening of epoxide in epoxidation and Mitsunobu reaction were used ingeniously as two key steps with high stereoselectivity.展开更多
An efficient and stereoselective four Step Synthesis of (-)Massoialactone (1) is described.The key step intolves deoxygenation of one α,β - unsatoted carbonyl group in compound
The stereoselective synthesis of (+)-preussin has been achieved by utilizing the Sharpless asymmetric epoxidation of the divinylcarbinol(3) and the oxidative cyclization of 9with PDC as the key steps.
1α- and 1β-methyl agarofuran 1 and 2 were stereoselectively synthesized. the key intermediates being synthesized through stereoselective Robinson annulation.The conjugated double bond was redined in an improved way....1α- and 1β-methyl agarofuran 1 and 2 were stereoselectively synthesized. the key intermediates being synthesized through stereoselective Robinson annulation.The conjugated double bond was redined in an improved way. Alkylation of imine 7 with enone 8, 9, 10 was展开更多
By previously reported modified Masai-Rausch method of synthesizing titanocenocycles,followed by acid hydrolysis,trisubstituted al-kenes were synthesized,yields obtained are higher than that reported in literatures.St...By previously reported modified Masai-Rausch method of synthesizing titanocenocycles,followed by acid hydrolysis,trisubstituted al-kenes were synthesized,yields obtained are higher than that reported in literatures.Starting from unsymmetrical alkyne substrates,twelve different types of substituted alkenes were synthesized,among which only two were found single component,others were of mixed isomers.Beside conventional analytical methods,the NMR spectral analysis of titanocenoheterocycle intermediates and the products were used to identify the isomeric structures as well as their relative contents.展开更多
The structure of syn- and anti-Nb-(p-toluenesulfonyl)-3a-hydroxyl-1, 2, 3, 3a, 8, 8a-hexahydro pyrrolo[2,3-b] indole-2-carboxylic t-butyl ester was stereoselectively synthesized by oxidative ring formation of Nb-(p-to...The structure of syn- and anti-Nb-(p-toluenesulfonyl)-3a-hydroxyl-1, 2, 3, 3a, 8, 8a-hexahydro pyrrolo[2,3-b] indole-2-carboxylic t-butyl ester was stereoselectively synthesized by oxidative ring formation of Nb-(p-toluenesulfonyl)-L-tryptophan t-butyl ester in methylene chloride containing dimethyldioxirane (DMDO), the p-toluenesulfonyl group and t-butyl group can be easily removed by sodium naphthalenide and trifluoroacetic acid, respectively.展开更多
Lignans are a powerful weapon for plants to resist stresses and have diverse bioactive functions to protect human health.Elucidating the mechanisms of stereoselective biosynthesis and response to stresses of lignans i...Lignans are a powerful weapon for plants to resist stresses and have diverse bioactive functions to protect human health.Elucidating the mechanisms of stereoselective biosynthesis and response to stresses of lignans is important for the guidance of plant improvement.Here,we identified the complete pathway to stereoselectively synthesize antiviral(-)-lariciresinol glucosides in Isatis indigotica roots,which consists of three-step sequential stereoselective enzymes DIR1/2,PLR,and UGT71B2.DIR1 was further identified as the key gene in respoJanuary 2024nse to stresses and was able to trigger stress defenses by mediating the elevation in lignan content.Mechanistically,the phytohormone-responsive ERF transcription factor LTF1 colocalized with DIR1 in the cell periphery of the vascular regions in mature roots and helped resist biotic and abiotic stresses by directly regulating the expression of DIR1.These systematic results suggest that DIR1 as the first common step of the lignan pathway cooperates with PLR and UGT71B2 to stereoselectively synthesize(-)-lariciresinol derived antiviral lignans in I.indigotica roots and is also a part of the LTF1-mediated regulatory network to resist stresses.In conclusion,the LTF1-DIR1 module is an ideal engineering target to improve plant Defenses while increasing the content of valuable lignans in plants.展开更多
A family of the 3,6-branched Fuziα-glucans including the pentasaccharide repeating unit as well as its di-and trimers were efficiently achieved via a one-pot and convergent glycosylation strategy.All the protectedα-...A family of the 3,6-branched Fuziα-glucans including the pentasaccharide repeating unit as well as its di-and trimers were efficiently achieved via a one-pot and convergent glycosylation strategy.All the protectedα-glucans up to 15-mer were assembled with high yields and excellentα-stereoselectivity,which was secured by the synergisticα-directing effects of the Tol SCl/Ag OTf promotion system and the stericβ-facial shielding of bulky saccharide residues linked at the 6-O-position of glucosyl donors.Moreover,the 3,6-branched architecture of glycosyl donor was revealed to be more favorable for theα-selective glucosidation of primary hydroxyl group,especially in the case of large oligosaccharide acceptor.The structurally well-defined syntheticα-glucans would be useful for various biological studies.展开更多
A series of new N-substituted iminosugars were successfully synthesized through a general synthetic route from D-xylose derivative.This approach provided a convenient access to the synthesis of N-alkylated iminosugars...A series of new N-substituted iminosugars were successfully synthesized through a general synthetic route from D-xylose derivative.This approach provided a convenient access to the synthesis of N-alkylated iminosugars as po-tential glucosidase inhibitors,which included a reaction of reductive amination.Various N-alkylated iminosugars were prepared in good yields with high stereoselectivity.展开更多
Aldols from aliphatic aldehydes had been synthesized enantioselectively using Singh’s catalyst. Self and crossed aldol reactions with several linear aldehydes were performed.
In recent years,the synthesis and application of alkenes have attracted increased attention.Triphenylethenes(TriPEs)have lower molecular torsion than tetraphenylethenes(TPEs),which helps to balance the degree of conju...In recent years,the synthesis and application of alkenes have attracted increased attention.Triphenylethenes(TriPEs)have lower molecular torsion than tetraphenylethenes(TPEs),which helps to balance the degree of conjugation and the aggregation-induced emission(AIE)effect.The geometry of double bonds has a significant impact on luminescence.Therefore,it is essential to provide a comprehensive summary of the stereoselective synthetic strategies for trisubstituted alkenes.In this review,common strategies for the stereoselective synthesis of alkenes are described,with an emphasis on the origin of stereoselectivity and the types of substrates.In addition,the AIE properties of TriPE and its applications in optoelectronic devices,stimuli-responsive materials,sensors,and therapies were discussed.展开更多
The evolution of synthetic design toward the efficient synthesis of cyclobutane natural product(±)-piperarborenine B is demonstrated.Taking the advantages of good functional group compatibility of contractive syn...The evolution of synthetic design toward the efficient synthesis of cyclobutane natural product(±)-piperarborenine B is demonstrated.Taking the advantages of good functional group compatibility of contractive synthesis of cyclobutanes from pyrrolidines,stereoselective synthesis of unsymmetric highly functionalized cyclobutanes core of(±)-piperarborenine B was realized in one step.Also,an unprecedented carboxylic acid assisted-diastereoselective Kracho decarboxylation/transmethylation features a new strategy for a non-symmetrical cyclobutane core.The synthesis of(±)-piperarborenine B illustrates the advancement of methodology resulting in the improvement in synthetic efficiency.展开更多
Luminescent materials with efficient aggregate-state emissions are of growing interest due to their widespread applications in chemo-/biosensing and optoelectronic devices.Aggregation-induced emission(AIE)opens a new ...Luminescent materials with efficient aggregate-state emissions are of growing interest due to their widespread applications in chemo-/biosensing and optoelectronic devices.Aggregation-induced emission(AIE)opens a new avenue for the applications of aggregate-state luminescent materials.Among the AIE luminogens(AIEgens),tetraarylethylenes(TAEs)are typical AIEgens with a simple molecule scaffold and could be utilized as a framework for further elaboration,enabling structure-property-function relationship studies and multi-functional applications.Since the existing approaches for the preparation of tetraarylethenes(TAEs)typically produce stereoisomeric mixtures,stereoselective synthesis of tetraarylethenes with desired geometry is a great challenge.In this review,we systematically compile the synthetic methodologies for the construction of TAEs in excellent regio-and stereoselectivities.The virtues and limitations of each methodology are discussed in detail as well.Meanwhile,the applications and the differences of properties between TAEs stereoisomers are introduced.展开更多
文摘The stereoselective synthesis of 2 -chloro-4- substituted-phenyl-5, 5-dimthyl- 1,3, 2-dioxaphsphorinan- 2 - (thi) ones is described. only single trans-isomers were obtained when 1-substituted-phenyl-2, 2 -dimethyl-1,3 -propanediols (1) reacted with POCl3. But the stereoselectivity of cyclization reaction between (1) and PSCl3, depended greatly upon the reaction condition. The configurational assignments and the ratio of cis-/trans-diastereoisomers of the products were performed on the basis of 1 HNMR, 31PNMR and IR spectra and confirmed by X-ray diffraction
基金the National Natural Science Foundation of China (No.29972015).
文摘1-(4-hydroxy-3-methoxyphenyl)-2-(4-formyl-2-methoxyphenoxy)-propane-1,3-diol, A 8-O-4’ neolignan, has been stereoselectively synthesized in eight steps from ferulic acid, and the directly cis opening of epoxide in epoxidation and Mitsunobu reaction were used ingeniously as two key steps with high stereoselectivity.
文摘An efficient and stereoselective four Step Synthesis of (-)Massoialactone (1) is described.The key step intolves deoxygenation of one α,β - unsatoted carbonyl group in compound
文摘The stereoselective synthesis of (+)-preussin has been achieved by utilizing the Sharpless asymmetric epoxidation of the divinylcarbinol(3) and the oxidative cyclization of 9with PDC as the key steps.
文摘1α- and 1β-methyl agarofuran 1 and 2 were stereoselectively synthesized. the key intermediates being synthesized through stereoselective Robinson annulation.The conjugated double bond was redined in an improved way. Alkylation of imine 7 with enone 8, 9, 10 was
文摘By previously reported modified Masai-Rausch method of synthesizing titanocenocycles,followed by acid hydrolysis,trisubstituted al-kenes were synthesized,yields obtained are higher than that reported in literatures.Starting from unsymmetrical alkyne substrates,twelve different types of substituted alkenes were synthesized,among which only two were found single component,others were of mixed isomers.Beside conventional analytical methods,the NMR spectral analysis of titanocenoheterocycle intermediates and the products were used to identify the isomeric structures as well as their relative contents.
基金financial supports from Bayer AGCompany and National Natural Science Foundation of China(Grant Number 30123005)CH thanks the DAAD for a scholarship from its program"Biowissenschaften"
文摘The structure of syn- and anti-Nb-(p-toluenesulfonyl)-3a-hydroxyl-1, 2, 3, 3a, 8, 8a-hexahydro pyrrolo[2,3-b] indole-2-carboxylic t-butyl ester was stereoselectively synthesized by oxidative ring formation of Nb-(p-toluenesulfonyl)-L-tryptophan t-butyl ester in methylene chloride containing dimethyldioxirane (DMDO), the p-toluenesulfonyl group and t-butyl group can be easily removed by sodium naphthalenide and trifluoroacetic acid, respectively.
基金The authors would like to acknowledge Professor Jiankang Zhu and his lab at the Shanghai Center for Plant Stress Biology,Chinese Center for Plant Stress Biology,for providing the CRISPR/Cas9 system plasmids.All authors declare no competing financial or nonfinancial interests.This work was funded by the National Natural Science Foundation of China(grant Nos.82225047,32000231,31970316,and 32170274)the National Key Research and Development Program of China(grant no.2022YFC3501703)+1 种基金Shanghai Science and Technology Development Funds(23QA1411400,China)Key project at central government level(The ability establishment of sustainable use for valuable Chinese medicine resources,2060302).
文摘Lignans are a powerful weapon for plants to resist stresses and have diverse bioactive functions to protect human health.Elucidating the mechanisms of stereoselective biosynthesis and response to stresses of lignans is important for the guidance of plant improvement.Here,we identified the complete pathway to stereoselectively synthesize antiviral(-)-lariciresinol glucosides in Isatis indigotica roots,which consists of three-step sequential stereoselective enzymes DIR1/2,PLR,and UGT71B2.DIR1 was further identified as the key gene in respoJanuary 2024nse to stresses and was able to trigger stress defenses by mediating the elevation in lignan content.Mechanistically,the phytohormone-responsive ERF transcription factor LTF1 colocalized with DIR1 in the cell periphery of the vascular regions in mature roots and helped resist biotic and abiotic stresses by directly regulating the expression of DIR1.These systematic results suggest that DIR1 as the first common step of the lignan pathway cooperates with PLR and UGT71B2 to stereoselectively synthesize(-)-lariciresinol derived antiviral lignans in I.indigotica roots and is also a part of the LTF1-mediated regulatory network to resist stresses.In conclusion,the LTF1-DIR1 module is an ideal engineering target to improve plant Defenses while increasing the content of valuable lignans in plants.
基金supported by the National Natural Science Foundation of China(No.22177060)the Young Scholars Program of Shandong University(No.2018WLJH41)+1 种基金the Open Projects Fund of Shandong Key Laboratory of Carbohydrate Chemistry and Glycobiology,Shandong University(No.2021CCG06)the Central Government Guide Local Science and Technology Development Funds(No.YDZX20203700002579)。
文摘A family of the 3,6-branched Fuziα-glucans including the pentasaccharide repeating unit as well as its di-and trimers were efficiently achieved via a one-pot and convergent glycosylation strategy.All the protectedα-glucans up to 15-mer were assembled with high yields and excellentα-stereoselectivity,which was secured by the synergisticα-directing effects of the Tol SCl/Ag OTf promotion system and the stericβ-facial shielding of bulky saccharide residues linked at the 6-O-position of glucosyl donors.Moreover,the 3,6-branched architecture of glycosyl donor was revealed to be more favorable for theα-selective glucosidation of primary hydroxyl group,especially in the case of large oligosaccharide acceptor.The structurally well-defined syntheticα-glucans would be useful for various biological studies.
基金This work was supported by the National Natural Science Foundation of China(Nos.21372215 and 20972151).
文摘A series of new N-substituted iminosugars were successfully synthesized through a general synthetic route from D-xylose derivative.This approach provided a convenient access to the synthesis of N-alkylated iminosugars as po-tential glucosidase inhibitors,which included a reaction of reductive amination.Various N-alkylated iminosugars were prepared in good yields with high stereoselectivity.
文摘Aldols from aliphatic aldehydes had been synthesized enantioselectively using Singh’s catalyst. Self and crossed aldol reactions with several linear aldehydes were performed.
基金supported by the National Natural Science Foundation of China(81874181,21871284)the Major Scientific and Technological Special Project for“Significant New Drugs Creation”(2019ZX09301158)+2 种基金the Emerging Frontier Program of Hospital Development Centre(SHDC12018107)the Science&Technology Department of Shanghai(18401933500)the State Key Laboratory of Bioorganic and Natural Products Chemistry。
文摘In recent years,the synthesis and application of alkenes have attracted increased attention.Triphenylethenes(TriPEs)have lower molecular torsion than tetraphenylethenes(TPEs),which helps to balance the degree of conjugation and the aggregation-induced emission(AIE)effect.The geometry of double bonds has a significant impact on luminescence.Therefore,it is essential to provide a comprehensive summary of the stereoselective synthetic strategies for trisubstituted alkenes.In this review,common strategies for the stereoselective synthesis of alkenes are described,with an emphasis on the origin of stereoselectivity and the types of substrates.In addition,the AIE properties of TriPE and its applications in optoelectronic devices,stimuli-responsive materials,sensors,and therapies were discussed.
基金A.P.A.thanks for the support of the DFG(No.AN 1064/4–1)and the Boehringer Ingelheim Foundation(Plus 3).C.H.thanks the International Max Planck Research School for Living Matter(Dortmund,Germany).
文摘The evolution of synthetic design toward the efficient synthesis of cyclobutane natural product(±)-piperarborenine B is demonstrated.Taking the advantages of good functional group compatibility of contractive synthesis of cyclobutanes from pyrrolidines,stereoselective synthesis of unsymmetric highly functionalized cyclobutanes core of(±)-piperarborenine B was realized in one step.Also,an unprecedented carboxylic acid assisted-diastereoselective Kracho decarboxylation/transmethylation features a new strategy for a non-symmetrical cyclobutane core.The synthesis of(±)-piperarborenine B illustrates the advancement of methodology resulting in the improvement in synthetic efficiency.
基金National Natural Science Foundation of China,Grant/Award Numbers:21971059,21702056National Program forThousandYoungTalents of ChinaFundamental Research Funds。
文摘Luminescent materials with efficient aggregate-state emissions are of growing interest due to their widespread applications in chemo-/biosensing and optoelectronic devices.Aggregation-induced emission(AIE)opens a new avenue for the applications of aggregate-state luminescent materials.Among the AIE luminogens(AIEgens),tetraarylethylenes(TAEs)are typical AIEgens with a simple molecule scaffold and could be utilized as a framework for further elaboration,enabling structure-property-function relationship studies and multi-functional applications.Since the existing approaches for the preparation of tetraarylethenes(TAEs)typically produce stereoisomeric mixtures,stereoselective synthesis of tetraarylethenes with desired geometry is a great challenge.In this review,we systematically compile the synthetic methodologies for the construction of TAEs in excellent regio-and stereoselectivities.The virtues and limitations of each methodology are discussed in detail as well.Meanwhile,the applications and the differences of properties between TAEs stereoisomers are introduced.