Transition metal-catalyzed asymmetric transfer hydrogenation has been proven to be a powerful approach for the synthesis of chiral alcohols.Herein,a highly efficient and enantioselective transfer hydrogenation of dibe...Transition metal-catalyzed asymmetric transfer hydrogenation has been proven to be a powerful approach for the synthesis of chiral alcohols.Herein,a highly efficient and enantioselective transfer hydrogenation of dibenzoheptaheterocyclic ketones catalyzed by an arene-tethered TsDPEN-based Rh(ll)catalyst has been successfully developed,and a variety of dibenzoheptaheterocyclic ketones were reduced by a 1/1 mixture of formic acid and DBU(1,8-diazabicyclo[5.4.0]undec-7-ene)with high yields and enantioselectivities.With this method,the asymmetric reduction of 7,8-difluorodibenzo[b,e]thiepin-11(6H)-one has been realized,providing the key intermediate of baloxavir marboxil with>99% yield and>99% ee at a substrate/catalyst molar ratio of 1000.展开更多
Doyle-Kirmse rearrangement reactions have received continuous attention as an important method for constructing complex chemical structures. Herein, we disclosed an efficient rhodium-catalyzed DoyleKirmse rearrangemen...Doyle-Kirmse rearrangement reactions have received continuous attention as an important method for constructing complex chemical structures. Herein, we disclosed an efficient rhodium-catalyzed DoyleKirmse rearrangement reaction, which can simultaneously construct C–C bonds and C–X(X = S/Se) bonds using sulfoxonium ylides as starting materials to obtain sulfur-or selenium-containing compounds. This strategy is characterized by the safer and greener carbene precursor, high yields and broad substrate scope, possessing a wide range of application.展开更多
基金the Southern University of Science and Technology(start-up fund),Shenzhen Science and Technology Innovation Committee(No.KQTD20150717103157174)Stable Support Plan Program of Shenzhen Natural Science Fund(Program Contract No.20200925161222002)+4 种基金Key-Area Research and DevelopmentPt rogramofGuangdong Province((No.2020B010188001)Innovative Team of Universities in Guangdong Province(No.2020KCXTD016)National Natural Science Foundation of China(No.21991113)the National Natural Science Foundation of China(No.22171129)Shenzhen Science and Technology Innovation Committee(JCYJ20210324104202007)for financial support.
文摘Transition metal-catalyzed asymmetric transfer hydrogenation has been proven to be a powerful approach for the synthesis of chiral alcohols.Herein,a highly efficient and enantioselective transfer hydrogenation of dibenzoheptaheterocyclic ketones catalyzed by an arene-tethered TsDPEN-based Rh(ll)catalyst has been successfully developed,and a variety of dibenzoheptaheterocyclic ketones were reduced by a 1/1 mixture of formic acid and DBU(1,8-diazabicyclo[5.4.0]undec-7-ene)with high yields and enantioselectivities.With this method,the asymmetric reduction of 7,8-difluorodibenzo[b,e]thiepin-11(6H)-one has been realized,providing the key intermediate of baloxavir marboxil with>99% yield and>99% ee at a substrate/catalyst molar ratio of 1000.
基金supported by Sichuan Science and Technology Program (No.2020YJ0221)。
文摘Doyle-Kirmse rearrangement reactions have received continuous attention as an important method for constructing complex chemical structures. Herein, we disclosed an efficient rhodium-catalyzed DoyleKirmse rearrangement reaction, which can simultaneously construct C–C bonds and C–X(X = S/Se) bonds using sulfoxonium ylides as starting materials to obtain sulfur-or selenium-containing compounds. This strategy is characterized by the safer and greener carbene precursor, high yields and broad substrate scope, possessing a wide range of application.
