An efficient synthesis of the electrophilic reagent,S-(1,3-dioxoisoindolin-2-yl)O,O-diethyl phosphorothioate(SDDP)is described.Moreover,the synthetic applications of SDDP wherein the transfer of the SP(O)(OEt)_(2) moi...An efficient synthesis of the electrophilic reagent,S-(1,3-dioxoisoindolin-2-yl)O,O-diethyl phosphorothioate(SDDP)is described.Moreover,the synthetic applications of SDDP wherein the transfer of the SP(O)(OEt)_(2) moiety occurs were investigated.In this manner,SDDP underwent facile SP(O)(OEt)_(2) transfer with electron-rich substrates such as ketones,indoles,and thiols to formα-phosphorothiolated ketones,3-phosphorothiolated indoles and S-phosphorothiolated thioethers,respectively.展开更多
Comprehensive Summary Metallacyclopentadienes play a vital role in transition-metal mediated and catalyzed cycloaddition reactions of alkynes.Though versatile reactions of metallacyclopentadienes with alkynes have bee...Comprehensive Summary Metallacyclopentadienes play a vital role in transition-metal mediated and catalyzed cycloaddition reactions of alkynes.Though versatile reactions of metallacyclopentadienes with alkynes have been disclosed,[2+1]cycloadditions of metallacyclopentadienes and alkynes have never been discovered.In present work,we report the formal[2+1]cycloadditions of a metallacyclopentadiene unit with a broad scope of commercial alkynes,providing a facile strategy to construct tetracyclic conjugated compounds.The deuterated experiment indicates a metal vinylidene intermediate has been involved in[2+1]cycloaddition.Moreover,the electrophilic substitution reaction of the tetracyclic conjugated compound with the aid of density functional theory(DFT)calculated Fukui functions is investigated.展开更多
Aromatic oxazolines are versatile in organic synthesis as directing groups,ligands,and protected carboxylic acids.Developing efficient approaches to oxazoline from an aromatic C−H bond is more desirable compared to th...Aromatic oxazolines are versatile in organic synthesis as directing groups,ligands,and protected carboxylic acids.Developing efficient approaches to oxazoline from an aromatic C−H bond is more desirable compared to the established protocols from carboxylic acid and its equivalents.Herein,a simple and efficient aromatic C−H oxazolination with broad substrate scope is described.By employing this transformation as an enabling step,diversity-oriented synthesis of functionalized arenes and target-oriented synthesis of four drugs were accomplished.Mechanistic experiments suggest that this aromatic oxazolination is an electrophilic aromatic substitution.It is anticipated that this transformation will find applications in aromatic C−H functionalization with oxazoline either as a removable directing group or as a masked carboxylic acid.展开更多
基金generous financial support by National Natural Science Foundation of China(No.21472133)the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)Key Laboratory of Organic Synthesis of Jiangsu Province(No.KJS1749).
文摘An efficient synthesis of the electrophilic reagent,S-(1,3-dioxoisoindolin-2-yl)O,O-diethyl phosphorothioate(SDDP)is described.Moreover,the synthetic applications of SDDP wherein the transfer of the SP(O)(OEt)_(2) moiety occurs were investigated.In this manner,SDDP underwent facile SP(O)(OEt)_(2) transfer with electron-rich substrates such as ketones,indoles,and thiols to formα-phosphorothiolated ketones,3-phosphorothiolated indoles and S-phosphorothiolated thioethers,respectively.
基金the National Natural Science Foundation of China(Nos.21931002,22071098,22101115,and 22101123)the Shenzhen Science and Technology Innovation Committee(Nos.JCYJ20200109140812302 and JCYJ20210324105013035)the Guangdong Provincial Key Laboratory of Catalysis(No.2020B121201002)。
文摘Comprehensive Summary Metallacyclopentadienes play a vital role in transition-metal mediated and catalyzed cycloaddition reactions of alkynes.Though versatile reactions of metallacyclopentadienes with alkynes have been disclosed,[2+1]cycloadditions of metallacyclopentadienes and alkynes have never been discovered.In present work,we report the formal[2+1]cycloadditions of a metallacyclopentadiene unit with a broad scope of commercial alkynes,providing a facile strategy to construct tetracyclic conjugated compounds.The deuterated experiment indicates a metal vinylidene intermediate has been involved in[2+1]cycloaddition.Moreover,the electrophilic substitution reaction of the tetracyclic conjugated compound with the aid of density functional theory(DFT)calculated Fukui functions is investigated.
基金the Fundamental Research Funds for the Central Universities(22qntd2306)Guangzhou Municipal Science and Technology Bureau(202201011151)the National Natural Science Foundation of China(22201311).
文摘Aromatic oxazolines are versatile in organic synthesis as directing groups,ligands,and protected carboxylic acids.Developing efficient approaches to oxazoline from an aromatic C−H bond is more desirable compared to the established protocols from carboxylic acid and its equivalents.Herein,a simple and efficient aromatic C−H oxazolination with broad substrate scope is described.By employing this transformation as an enabling step,diversity-oriented synthesis of functionalized arenes and target-oriented synthesis of four drugs were accomplished.Mechanistic experiments suggest that this aromatic oxazolination is an electrophilic aromatic substitution.It is anticipated that this transformation will find applications in aromatic C−H functionalization with oxazoline either as a removable directing group or as a masked carboxylic acid.
