The stereoselectivity of some Diels-Alder reactions was investigated by means of ABEEM-oTr model. Combined with local hard-soft and acid-base （HSAB） principle, we made reasonable explanation by calculating local sof...The stereoselectivity of some Diels-Alder reactions was investigated by means of ABEEM-oTr model. Combined with local hard-soft and acid-base （HSAB） principle, we made reasonable explanation by calculating local softness of atom and bond regions for the stereoselectivity of four Diels-Alder reactions involving cyclopentadiene.展开更多
Molecular structures of reactants were characterized by molecular electronegativity distance vector （VHMED） considering hydrogen association. A reasonable molecular modeling equation with 4-parameters was achieved f...Molecular structures of reactants were characterized by molecular electronegativity distance vector （VHMED） considering hydrogen association. A reasonable molecular modeling equation with 4-parameters was achieved for quantitative structure-property/activity relationship （QSPR/QSAR） by stepwise multiple regression （SMR） that the variable was introduced item by item in significant level order. A high correlation coefficient （R = 0.980） demonstrates that the model is able to well express a quantitative relation between stereoselectivity and the reactant structures as quantitative structure-reactivity/stereoselectivity relationship （QSRR/QSSR）. The multiple correlation coefficient （Rcv= 0.964） was tested through cross-validation with the leave-one-out （LOO） procedure. The above results show that the model possesses high estimation stability and good prediction ability between the amount of both cis and trans isomers in products and reactants.展开更多
(R)-1,3-butanediol is an important pharmaceutical intermediate, and the synthesis of(R)-1,3-butanediol using green biological methods has recently been of interest for industrial application. Here, a novel strain QC-1...(R)-1,3-butanediol is an important pharmaceutical intermediate, and the synthesis of(R)-1,3-butanediol using green biological methods has recently been of interest for industrial application. Here, a novel strain QC-1 that efficiently transforms 4-hydroxy-2-butanone to(R)-1,3-butanediol was isolated from soil samples. Based on morphological, physiological, and biochemical tests and 5.8 S-internal transcribed spacer sequencing, the strain was identified as Pichia kudriavzevii QC-1. The reaction conditions were optimized to 35 ℃, pH 8.0, rotation speed 200 rpm, and 6:5 mass ratio of glucose to 4-hydroxy-2-butanone. Evaluation of the effects of 4-hydroxy-2-butanone concentrations on yield and cell survival rate showed that 85.60 g·L^-1 product accumulated, with an enantiomeric excess of more than 99%, when 30 g·L^-14-hydroxy-2-butanone was added at 0, 10, and 30 h in a 3-L bioreactor. Thus, strain QC-1 showed excellent catalytic activity and stereoselectivity for the synthesis of(R)-1,3-butanediol from 4-hydroxy-2-butanone.展开更多
3-Deoxy-D-manno–oct-2-ulosonic acid(Kdo)is widely distributed in bacteria,and the synthesis of Kdocontaining oligosaccharides is important for the development of novel antibiotics and immunological agents.We have rec...3-Deoxy-D-manno–oct-2-ulosonic acid(Kdo)is widely distributed in bacteria,and the synthesis of Kdocontaining oligosaccharides is important for the development of novel antibiotics and immunological agents.We have recently developed a strategy to achieveα-stereocontrolled glycosylation using a C3-p-tolylthio-substituted Kdo phosphite donor.The wide substrate scope and high reactivity of the donors enabled the efficient synthesis of a series of Kdo-containing glycosides with completeα-stereoselectivity and without the formation of 2,3-ene byproducts.In this study,we improved the method by replacing the leaving group diethyl phosphite with fluoride,which enhanced the stability of the donor and led to cleaner reaction.Furthermore,the substrate range was expanded by synthesizing a series of Kdo O/C/S/Nglycosides,which also opened up a new avenue for the synthesis of CMP-Kdo synthase inhibitors.展开更多
The authors regret that in the original article,the structure of(–)-swainsonine(1)in Graphical abstract,Fig.1,Schemes 1 and 3 was incorrect.The correct structure is shown here.
基金the grants from the National Natural Science Foundation of China.(No.20633050 and 20403007).
文摘The stereoselectivity of some Diels-Alder reactions was investigated by means of ABEEM-oTr model. Combined with local hard-soft and acid-base （HSAB） principle, we made reasonable explanation by calculating local softness of atom and bond regions for the stereoselectivity of four Diels-Alder reactions involving cyclopentadiene.
文摘Molecular structures of reactants were characterized by molecular electronegativity distance vector （VHMED） considering hydrogen association. A reasonable molecular modeling equation with 4-parameters was achieved for quantitative structure-property/activity relationship （QSPR/QSAR） by stepwise multiple regression （SMR） that the variable was introduced item by item in significant level order. A high correlation coefficient （R = 0.980） demonstrates that the model is able to well express a quantitative relation between stereoselectivity and the reactant structures as quantitative structure-reactivity/stereoselectivity relationship （QSRR/QSSR）. The multiple correlation coefficient （Rcv= 0.964） was tested through cross-validation with the leave-one-out （LOO） procedure. The above results show that the model possesses high estimation stability and good prediction ability between the amount of both cis and trans isomers in products and reactants.
基金Financial supports from the National Key R&D Program of China(2018YFC1604100)the National Natural Science Foundation of China(NSFC)[21676120,31872891]+8 种基金the 111 Project[111-2-06]the Highend Foreign Experts Recruitment Program[G20190010083]the Program for Advanced Talents within Six Industries of Jiangsu Province[2015-NY007]the National Program for Support of Top-notch Young Professionalsthe Fundamental Research Funds for the Central Universities[JUSRP51504]the Project Funded by the Priority Academic Program Development of Jiangsu Higher Education InstitutionsTop-notch Academic Programs Project of Jiangsu Higher Education Institutionsthe Jiangsu Province“Collaborative Innovation Center for Advanced Industrial Fermentation”Industry Development Programthe National First-Class Discipline Program of Light Industry Technology and Engineering[LITE2018-09]。
文摘(R)-1,3-butanediol is an important pharmaceutical intermediate, and the synthesis of(R)-1,3-butanediol using green biological methods has recently been of interest for industrial application. Here, a novel strain QC-1 that efficiently transforms 4-hydroxy-2-butanone to(R)-1,3-butanediol was isolated from soil samples. Based on morphological, physiological, and biochemical tests and 5.8 S-internal transcribed spacer sequencing, the strain was identified as Pichia kudriavzevii QC-1. The reaction conditions were optimized to 35 ℃, pH 8.0, rotation speed 200 rpm, and 6:5 mass ratio of glucose to 4-hydroxy-2-butanone. Evaluation of the effects of 4-hydroxy-2-butanone concentrations on yield and cell survival rate showed that 85.60 g·L^-1 product accumulated, with an enantiomeric excess of more than 99%, when 30 g·L^-14-hydroxy-2-butanone was added at 0, 10, and 30 h in a 3-L bioreactor. Thus, strain QC-1 showed excellent catalytic activity and stereoselectivity for the synthesis of(R)-1,3-butanediol from 4-hydroxy-2-butanone.
基金supported by the National Key R&D Program of China(Nos.2022YFF1203005,2022YFC2303700)supported by the National Natural Science Foundation of China(Nos.81930097,82151223).
文摘3-Deoxy-D-manno–oct-2-ulosonic acid(Kdo)is widely distributed in bacteria,and the synthesis of Kdocontaining oligosaccharides is important for the development of novel antibiotics and immunological agents.We have recently developed a strategy to achieveα-stereocontrolled glycosylation using a C3-p-tolylthio-substituted Kdo phosphite donor.The wide substrate scope and high reactivity of the donors enabled the efficient synthesis of a series of Kdo-containing glycosides with completeα-stereoselectivity and without the formation of 2,3-ene byproducts.In this study,we improved the method by replacing the leaving group diethyl phosphite with fluoride,which enhanced the stability of the donor and led to cleaner reaction.Furthermore,the substrate range was expanded by synthesizing a series of Kdo O/C/S/Nglycosides,which also opened up a new avenue for the synthesis of CMP-Kdo synthase inhibitors.
文摘The authors regret that in the original article,the structure of(–)-swainsonine(1)in Graphical abstract,Fig.1,Schemes 1 and 3 was incorrect.The correct structure is shown here.
