Summary:In various autoimmune diseases,Galecin-9(Gal-9)has been shown to regulate the T-cell balance by decreasing Th1 and Th17,while increasing the number of regulatory T cells(Tregs).However,the role of Gal-9 in the...Summary:In various autoimmune diseases,Galecin-9(Gal-9)has been shown to regulate the T-cell balance by decreasing Th1 and Th17,while increasing the number of regulatory T cells(Tregs).However,the role of Gal-9 in the patients with acute coronary syndrome(ACS)and chronic kidney disease(CKD)remains unclear.This study aims to measure the Gal-9 levels in serum and peripheral blood mononuclear cells(PBMCs)in patients with ACS plus CKD and examine their clinical implication.The serum levels of Gal-9 were determined by enzyme linked immunosorbent assay(ELISA),the expression levels of Gal-9,Tim-3,and Foxp3 mRNA in PBMCs were detected by real-time reverse transcription-polymerase chain reaction(RT-PCR),and the expression of Gal-9 on the surface of PBMCs and in PBMCs was analyzed by flow cytometry.Furthermore,the correlation of serum Gal-9 levels with anthropometric and biochemical variables in patients with ACS plus CKD was analyzed.The lowest levels of Gal-9 in serum and PBMCs were found in the only ACS group,followed by the ACS+CKD group,and the normal coronary artery(NCA)group,.respectively.Serum Gal-9 levels were increased along with the progression of glomerular filtration rate(GFR)categories of G1 to G4.Additionally,serum Gal-9 levels were negatively correlated with high-sensitivity C-reactive protein(hs-CRP),estimated GFR(eGFR),and lipoprotein(a),but positively with creatinine,age,osmotic pressure,and blood urea nitrogen(BUN).Notably,serum Gal-9 was independently associated with hs-CRP,osmotic pressure,and lipoprotein(a).Furthermore,serum Gal-9 levels were elevated in patients with type 2 diabetes(T2DM)and impaired glucose tolerance(IGT)in ACS group.It was suggested that the levels of Gal-9 in serum and PBMCs were decreased in patients with simple ACS and those with ACS plus CKD,and hs-CRP,eGFR,osmotic pressure and T2DM may have an influence on serum Gal-9 levels.展开更多
The design and synthesis of spirochroman-2-on-4,1'-indan-7'-ol(SCIOL)and its application for synthesizing chiral monophosphinite ligands are reported.The synthesis features a tandem double Friedel-Crafts react...The design and synthesis of spirochroman-2-on-4,1'-indan-7'-ol(SCIOL)and its application for synthesizing chiral monophosphinite ligands are reported.The synthesis features a tandem double Friedel-Crafts reaction/lactonization to construct the spiro framework and the desired racemic SCiOL was obtained via 6 steps with a total yield of 44.5%.Using an inclusion resolution with N-benzylcinchonidinium chloride,the optical SCiOL could be obtained in good yields on a gram scale.The preliminary studies indicated that the corresponding chiral spiro monophosphinite ligands exhibit high catalytic activity and enantioselectivity(up to 94%ee)in the rhodium-catalyzed asymmetric hydrogenation of N-acetyl dehydroamino esters.These outcomes highlight the significant potential of SCiOLas a useful framework forthedevelopment of chiral spiro ligands.展开更多
We report an enantioselective hydroarylation reaction of styrenes and 1,3-dienes with arylboronic acids catalyzed by nickel complexes bearing chiral spiro amino phosphine ligands.The reaction serves as an efficient,st...We report an enantioselective hydroarylation reaction of styrenes and 1,3-dienes with arylboronic acids catalyzed by nickel complexes bearing chiral spiro amino phosphine ligands.The reaction serves as an efficient,straightf orward,and mild method for the preparation of enantio enriched 1,1-diarylalkanes,which are important building blocks for the synthesis of many biologically active molecules.This redox neutral reaction uses only catalytic amounts of the reagents and is,therefore,atom economical and environmentally benign.展开更多
The regio-and enantioselective functionalization of 1,3-dienes has become a powerful tool for the synthesis of allylic compounds,yet it remains a challenge for aliphatic dienes.Herein,we report a nickel-catalyzed asym...The regio-and enantioselective functionalization of 1,3-dienes has become a powerful tool for the synthesis of allylic compounds,yet it remains a challenge for aliphatic dienes.Herein,we report a nickel-catalyzed asymmetric hydroarylation reaction of aliphatic and aromatic dienes with indoles to afford chiral indole derivatives.展开更多
Esters are abundant in natural and synthetic products and their conversion into primary alcohols holds great importance in fine chemical synthesis.However,achieving asymmetric hydrogenation(AH)of racemic esters with r...Esters are abundant in natural and synthetic products and their conversion into primary alcohols holds great importance in fine chemical synthesis.However,achieving asymmetric hydrogenation(AH)of racemic esters with remote stereocenters via kinetic resolution(KR)remains a formidable challenge due to the difficulties associated with discerning spatially distant stereocenters.To address this issue,we have designed a hydroxy-assisted strategy that introduces a hydroxy group into racemicβ-aryl esters to facilitate hydrogenation and enhance chiral discrimination through a lactone form.By employing chiral Ir-SpiroPAP catalysts,we achieved exceptional AH of racemic 4-substituted chroman-2-ones,lactone form of ortho-hydroxylatedβ-aryl esters,via KR,resulting in impressive selectivity factor(s)values of up to 600.This approach exhibited significant efficacy for racemic chroman-2-ones containingβ-aryl,alkenyl,alkynyl,and alkyl groups,enabling the synthesis of chiralγ-aryl primary alcohols and the recovery of chiralβ-aryl esters or chroman-2-ones,typically difficult to access using existing methods.The scalability and broad synthetic applications of this method were exemplified by successfully synthesizing chiral drugs(R)-fesoterodine and enrasentan,alongside various chiral intermediates essential for producing chiral drugs and natural products.These promising results highlight the potential of this approach as a powerful tool for synthesizing valuable chiral compounds.展开更多
基金This project was supported by grants from National Natural Science Foundation of China(No.81270354)Natural Science for Youth Foundation(No.81300213).
文摘Summary:In various autoimmune diseases,Galecin-9(Gal-9)has been shown to regulate the T-cell balance by decreasing Th1 and Th17,while increasing the number of regulatory T cells(Tregs).However,the role of Gal-9 in the patients with acute coronary syndrome(ACS)and chronic kidney disease(CKD)remains unclear.This study aims to measure the Gal-9 levels in serum and peripheral blood mononuclear cells(PBMCs)in patients with ACS plus CKD and examine their clinical implication.The serum levels of Gal-9 were determined by enzyme linked immunosorbent assay(ELISA),the expression levels of Gal-9,Tim-3,and Foxp3 mRNA in PBMCs were detected by real-time reverse transcription-polymerase chain reaction(RT-PCR),and the expression of Gal-9 on the surface of PBMCs and in PBMCs was analyzed by flow cytometry.Furthermore,the correlation of serum Gal-9 levels with anthropometric and biochemical variables in patients with ACS plus CKD was analyzed.The lowest levels of Gal-9 in serum and PBMCs were found in the only ACS group,followed by the ACS+CKD group,and the normal coronary artery(NCA)group,.respectively.Serum Gal-9 levels were increased along with the progression of glomerular filtration rate(GFR)categories of G1 to G4.Additionally,serum Gal-9 levels were negatively correlated with high-sensitivity C-reactive protein(hs-CRP),estimated GFR(eGFR),and lipoprotein(a),but positively with creatinine,age,osmotic pressure,and blood urea nitrogen(BUN).Notably,serum Gal-9 was independently associated with hs-CRP,osmotic pressure,and lipoprotein(a).Furthermore,serum Gal-9 levels were elevated in patients with type 2 diabetes(T2DM)and impaired glucose tolerance(IGT)in ACS group.It was suggested that the levels of Gal-9 in serum and PBMCs were decreased in patients with simple ACS and those with ACS plus CKD,and hs-CRP,eGFR,osmotic pressure and T2DM may have an influence on serum Gal-9 levels.
基金We thank the National Key R&D Program of China(2021YFA1500200)the National Natural Science Foundation of China(92056105,92256303,22221002,and 22188101)the Haihe Laboratory of Sustainable Chemical Transformations,the Fundamental Research Funds for the Central Universities,and the Frontiers Sciences Center for New Organic Matter at Nankai University(63181206)for financial support.
文摘The design and synthesis of spirochroman-2-on-4,1'-indan-7'-ol(SCIOL)and its application for synthesizing chiral monophosphinite ligands are reported.The synthesis features a tandem double Friedel-Crafts reaction/lactonization to construct the spiro framework and the desired racemic SCiOL was obtained via 6 steps with a total yield of 44.5%.Using an inclusion resolution with N-benzylcinchonidinium chloride,the optical SCiOL could be obtained in good yields on a gram scale.The preliminary studies indicated that the corresponding chiral spiro monophosphinite ligands exhibit high catalytic activity and enantioselectivity(up to 94%ee)in the rhodium-catalyzed asymmetric hydrogenation of N-acetyl dehydroamino esters.These outcomes highlight the significant potential of SCiOLas a useful framework forthedevelopment of chiral spiro ligands.
基金The authors thank the National Natural Science Founda-tion of China(Grant#s.21790332 and 21532003)the“111”project(Grant#B06005)of the Ministry of Educa-tion of China for their financial support.
文摘We report an enantioselective hydroarylation reaction of styrenes and 1,3-dienes with arylboronic acids catalyzed by nickel complexes bearing chiral spiro amino phosphine ligands.The reaction serves as an efficient,straightf orward,and mild method for the preparation of enantio enriched 1,1-diarylalkanes,which are important building blocks for the synthesis of many biologically active molecules.This redox neutral reaction uses only catalytic amounts of the reagents and is,therefore,atom economical and environmentally benign.
基金We thank the National Natural Science Foundation of China （Nos. 21790332, 21532003） and the ＂111＂ project （B06005） of the Ministry of Education of China for financial support.
基金the National Natural Science Foundation of China(nos.21790330 and 91956000)and the“111”Project(no.B06005)of the Ministry of Education of China for financial support.
文摘The regio-and enantioselective functionalization of 1,3-dienes has become a powerful tool for the synthesis of allylic compounds,yet it remains a challenge for aliphatic dienes.Herein,we report a nickel-catalyzed asymmetric hydroarylation reaction of aliphatic and aromatic dienes with indoles to afford chiral indole derivatives.
基金supported by the National Key R&D Program of China(grant no.2021YFA1500200)the National Natural Science Foundation of China(grant nos.92056105,92256303,22221002,and 22188101)the Fundamental Research Funds for the Central Universities,China,and the Haihe Laboratory of Sustainable Chemical Transformations,China.
文摘Esters are abundant in natural and synthetic products and their conversion into primary alcohols holds great importance in fine chemical synthesis.However,achieving asymmetric hydrogenation(AH)of racemic esters with remote stereocenters via kinetic resolution(KR)remains a formidable challenge due to the difficulties associated with discerning spatially distant stereocenters.To address this issue,we have designed a hydroxy-assisted strategy that introduces a hydroxy group into racemicβ-aryl esters to facilitate hydrogenation and enhance chiral discrimination through a lactone form.By employing chiral Ir-SpiroPAP catalysts,we achieved exceptional AH of racemic 4-substituted chroman-2-ones,lactone form of ortho-hydroxylatedβ-aryl esters,via KR,resulting in impressive selectivity factor(s)values of up to 600.This approach exhibited significant efficacy for racemic chroman-2-ones containingβ-aryl,alkenyl,alkynyl,and alkyl groups,enabling the synthesis of chiralγ-aryl primary alcohols and the recovery of chiralβ-aryl esters or chroman-2-ones,typically difficult to access using existing methods.The scalability and broad synthetic applications of this method were exemplified by successfully synthesizing chiral drugs(R)-fesoterodine and enrasentan,alongside various chiral intermediates essential for producing chiral drugs and natural products.These promising results highlight the potential of this approach as a powerful tool for synthesizing valuable chiral compounds.
