1 Introduction Heteroatom-stabilized carbenium ions have been widely recognized as potential electrophilic reagents.However,in contrast with the extensive works on thionium ion series,the highly labile character of se...1 Introduction Heteroatom-stabilized carbenium ions have been widely recognized as potential electrophilic reagents.However,in contrast with the extensive works on thionium ion series,the highly labile character of selenoxide functionalities has caused serious limitation in the synthetic use in spite of their wide potentiality as synthetic equivalents of electrophilic selonium ions.In this paper,novel generation of selonium ions and the synthetic uses of the species for Pummerer-typeα-functionalization and for cycloaddition by using the novel dienophilic behavior ofπ-conjugated selonium cations.展开更多
C-aryl glycosides are an important kind of carbohydrate derivatives for drug discovery,due to their distinctive attributes of resistance to hydrolysis from enzymes.Herein,C-aryl glycosylation was established for the s...C-aryl glycosides are an important kind of carbohydrate derivatives for drug discovery,due to their distinctive attributes of resistance to hydrolysis from enzymes.Herein,C-aryl glycosylation was established for the synthesis of 2-sulfur C-aryl glycals and 1,2-dihydrobenzofuran-fused C-aryl glycosides via interrupted Pummerer process,featured with sulfonium-tethered[3,3]-sigmatropic rearrangement between sulfoxide glycals and phenols.This protocol offers a broad substrate scope with diverse glycosyl and phenols.Dapagliflozin,Empagliflozin,and Ipragliflozin analogs were straightforward achieved,respectively.展开更多
The preparation of several functionalized furan derivatives and attempts to transform them into a derivative containing 6H-furo[3,4-b]furanone skeleton towards the construction of naphtho[2,3-b] furan are described. A...The preparation of several functionalized furan derivatives and attempts to transform them into a derivative containing 6H-furo[3,4-b]furanone skeleton towards the construction of naphtho[2,3-b] furan are described. Attempted Pummerer reaction of a furan sulfoxide derivative produced four interesting furan derivatives. Base promoted annulation between methyl 2-(phenylsulfinylmethyl)-3-furoate and 2-cyclohexenone proceeded to give dihydro naphtho[2,3-b]furanone derivative in a regiospecific manner.展开更多
Main observation and conclusion The reaction of 2-alkynylanisoles/sulfides with SOCl_(2) and DMSO was conducted to conveniently furnish the biologically interesting 3-(methylthio)-benzo[b]furans/thiophenes via intramo...Main observation and conclusion The reaction of 2-alkynylanisoles/sulfides with SOCl_(2) and DMSO was conducted to conveniently furnish the biologically interesting 3-(methylthio)-benzo[b]furans/thiophenes via intramolecular cyclization.DMSO acts as a solvent as well as a sulfur source and can also be replaced with DMSO-d_(6),enabling the incorporation of the SCD3 moiety of DMSO-d_(6) to the 3-position of the heterocyclic frameworks.展开更多
A series of 2-aryl-3-(4,5,6-trimethylpyrimidin-2-yl)thiazolidin-4-ones(1a–1c)and their derivatives bearing a lipophilic substituent,like acetoxy group(3a–3c),propionyloxy group(4a–4c),methyl(5d and 5e)at C-5 on thi...A series of 2-aryl-3-(4,5,6-trimethylpyrimidin-2-yl)thiazolidin-4-ones(1a–1c)and their derivatives bearing a lipophilic substituent,like acetoxy group(3a–3c),propionyloxy group(4a–4c),methyl(5d and 5e)at C-5 on thiazolidin-4-one ring were designed,synthesized and evaluated for their HIV-RT inhibitory activity.Using self-catalyzed Pummerer reaction,compounds 3a–3c and 4a–4c were obtained in good yield(63.1%–75.2%).Prelimin-ary anti-HIV-RT test of these derivatives indicated that compounds 1a–1c,4b(propionyloxy group at C-5)showed moderate HIV-RT inhibitory activity and com-pounds 5d and 5e with methyl at C-5 showed a weak HIV-RT inhibitory activity.Structure activity relationship analysis suggested that the substituted groups on C-5 would be unfavorable to anti-HIV-RT activity and that the steric effect might play a critical role in the anti-HIV RT activity.展开更多
文摘1 Introduction Heteroatom-stabilized carbenium ions have been widely recognized as potential electrophilic reagents.However,in contrast with the extensive works on thionium ion series,the highly labile character of selenoxide functionalities has caused serious limitation in the synthetic use in spite of their wide potentiality as synthetic equivalents of electrophilic selonium ions.In this paper,novel generation of selonium ions and the synthetic uses of the species for Pummerer-typeα-functionalization and for cycloaddition by using the novel dienophilic behavior ofπ-conjugated selonium cations.
基金The authors are grateful for financial support provided by NSFC(22125103and21971065)STCSM(22JC1401000,20xD1421500 and 20JC1416800)the Fundamental Research FundsfortheCentral Universities.
文摘C-aryl glycosides are an important kind of carbohydrate derivatives for drug discovery,due to their distinctive attributes of resistance to hydrolysis from enzymes.Herein,C-aryl glycosylation was established for the synthesis of 2-sulfur C-aryl glycals and 1,2-dihydrobenzofuran-fused C-aryl glycosides via interrupted Pummerer process,featured with sulfonium-tethered[3,3]-sigmatropic rearrangement between sulfoxide glycals and phenols.This protocol offers a broad substrate scope with diverse glycosyl and phenols.Dapagliflozin,Empagliflozin,and Ipragliflozin analogs were straightforward achieved,respectively.
文摘The preparation of several functionalized furan derivatives and attempts to transform them into a derivative containing 6H-furo[3,4-b]furanone skeleton towards the construction of naphtho[2,3-b] furan are described. Attempted Pummerer reaction of a furan sulfoxide derivative produced four interesting furan derivatives. Base promoted annulation between methyl 2-(phenylsulfinylmethyl)-3-furoate and 2-cyclohexenone proceeded to give dihydro naphtho[2,3-b]furanone derivative in a regiospecific manner.
基金We acknowledge the National Natural Science Foundation of China(No.21472136)for financial support.
文摘Main observation and conclusion The reaction of 2-alkynylanisoles/sulfides with SOCl_(2) and DMSO was conducted to conveniently furnish the biologically interesting 3-(methylthio)-benzo[b]furans/thiophenes via intramolecular cyclization.DMSO acts as a solvent as well as a sulfur source and can also be replaced with DMSO-d_(6),enabling the incorporation of the SCD3 moiety of DMSO-d_(6) to the 3-position of the heterocyclic frameworks.
基金financial support from the National Natural Science Foundation of China(Grant No.20672027)the Natural Science Foundation of Hebei Province(2008000588)are gratefully acknowledged.
文摘A series of 2-aryl-3-(4,5,6-trimethylpyrimidin-2-yl)thiazolidin-4-ones(1a–1c)and their derivatives bearing a lipophilic substituent,like acetoxy group(3a–3c),propionyloxy group(4a–4c),methyl(5d and 5e)at C-5 on thiazolidin-4-one ring were designed,synthesized and evaluated for their HIV-RT inhibitory activity.Using self-catalyzed Pummerer reaction,compounds 3a–3c and 4a–4c were obtained in good yield(63.1%–75.2%).Prelimin-ary anti-HIV-RT test of these derivatives indicated that compounds 1a–1c,4b(propionyloxy group at C-5)showed moderate HIV-RT inhibitory activity and com-pounds 5d and 5e with methyl at C-5 showed a weak HIV-RT inhibitory activity.Structure activity relationship analysis suggested that the substituted groups on C-5 would be unfavorable to anti-HIV-RT activity and that the steric effect might play a critical role in the anti-HIV RT activity.
