Chiral silyl ethers and silanols are important synthetic intermediates and bioactive compounds.In this work,we developed a onepot remote desymmetrization/Peterson-olefination of silacyclopentene oxides with benzoic ac...Chiral silyl ethers and silanols are important synthetic intermediates and bioactive compounds.In this work,we developed a onepot remote desymmetrization/Peterson-olefination of silacyclopentene oxides with benzoic acids in the presence of Martin’s sulfurane.This new methodology not only realizes the atom-economy of Peterson olefination,but also represents a catalytic method for synthesis of silicon-stereogenic silyl ethers.Using a bulky chiral phosphoric acid 4i as organocatalyst,the reactions proceeded efficiently to afford various olefin-functionalized organosilyl ethers in excellent diastereoelectivities(up to 25/1 d.r.)and high enantioselectivities(up to 94%ee).展开更多
Hydrosilylation is one of the most important reactions in synthetic chemistry and ranks as a fundamental method to access organosilicon compounds in industrial and academic processes.However,the enantioselective const...Hydrosilylation is one of the most important reactions in synthetic chemistry and ranks as a fundamental method to access organosilicon compounds in industrial and academic processes.However,the enantioselective construction of chiral-at-silicon compounds via catalytic asymmetric hydrosilylation remained limited and difficult.Here we report a highly enantioselective hydrosilylation of ynones,a type of carbonyl-activated alkynes,using a palladium catalyst with a chiral binaphthyl phosphoramidite ligand.The stereospecific hydrosilylation of ynones affords a series of silicon-stereogenic silylenones with up to 94%yield,>20:1 regioselectivity and 98:2 enantioselectivity.The density functional theory(DFT)calculations were conducted to elucidate the reaction mechanism and origin of high degree of stereoselectivity,in which the powerful potential of aromatic interaction in this reaction is highlighted by the multiple C–H-πinteraction and aromatic cavity-oriented enantioselectivitydetermining step during desymmetric functionalization of Si–H bond.展开更多
基金supported by the National Natural Science Foundation of China(22271276,21871254,21702203)the National Key Research and Development Program of China(2022YFC2105900)。
文摘Chiral silyl ethers and silanols are important synthetic intermediates and bioactive compounds.In this work,we developed a onepot remote desymmetrization/Peterson-olefination of silacyclopentene oxides with benzoic acids in the presence of Martin’s sulfurane.This new methodology not only realizes the atom-economy of Peterson olefination,but also represents a catalytic method for synthesis of silicon-stereogenic silyl ethers.Using a bulky chiral phosphoric acid 4i as organocatalyst,the reactions proceeded efficiently to afford various olefin-functionalized organosilyl ethers in excellent diastereoelectivities(up to 25/1 d.r.)and high enantioselectivities(up to 94%ee).
基金This work was supported by the National Natural Science Foundation of China(21773051,22072035,21703051,21801056,21901056)Zhejiang Provincial Natural Science Foundation of China(LZ18B020001,LY18B020013,LQ19B040001).
文摘Hydrosilylation is one of the most important reactions in synthetic chemistry and ranks as a fundamental method to access organosilicon compounds in industrial and academic processes.However,the enantioselective construction of chiral-at-silicon compounds via catalytic asymmetric hydrosilylation remained limited and difficult.Here we report a highly enantioselective hydrosilylation of ynones,a type of carbonyl-activated alkynes,using a palladium catalyst with a chiral binaphthyl phosphoramidite ligand.The stereospecific hydrosilylation of ynones affords a series of silicon-stereogenic silylenones with up to 94%yield,>20:1 regioselectivity and 98:2 enantioselectivity.The density functional theory(DFT)calculations were conducted to elucidate the reaction mechanism and origin of high degree of stereoselectivity,in which the powerful potential of aromatic interaction in this reaction is highlighted by the multiple C–H-πinteraction and aromatic cavity-oriented enantioselectivitydetermining step during desymmetric functionalization of Si–H bond.
