Oxidation is a fundamental reaction in organic chemistry and represents a unique strategy to convert starting materials with low oxidation states to new compounds with high oxidation states.Asymmetric oxidation is reg...Oxidation is a fundamental reaction in organic chemistry and represents a unique strategy to convert starting materials with low oxidation states to new compounds with high oxidation states.Asymmetric oxidation is regarded as the most straightforward protocol to prepare chiral oxides with high oxidation states and has played a crucial role in the fields of organic synthesis,material science and the pharmaceutical industry.However,previous studies typically focused on several specific substrates,such as alkenes,alcohols,and ketones,which have been well summarized in many reviews.Exploration of new substrate categories and reaction patterns remains a major challenge in this field.During the last decade,considerable progress has been made in non-enzymatic catalyzed asymmetric oxidations of C(sp^(3))-H bonds and heteroatoms.These advancements have facilitated the creation of diverse chiral molecules exhibiting excellent chemoselectivity and stereoselectivity.In this review,we summarize the progress in catalytic asymmetric oxidation of C(sp^(3))-H bonds and heteroatoms during the past decade,which would provide insights into challenging issues and enable future development.展开更多
A variety of phenyl alkyl sulfides were oxidized enantioselectively with NaIO_4 in chiral micellar systems formed from eight chiral surfactants,to give optical active sulfoxides.The enantiomer excesses ranged from 1.6...A variety of phenyl alkyl sulfides were oxidized enantioselectively with NaIO_4 in chiral micellar systems formed from eight chiral surfactants,to give optical active sulfoxides.The enantiomer excesses ranged from 1.6 to 15.0%.To understand the mechanistic detail of this asymmetric oxi- dation in chiral micelle,the effects of structure both in substrates and surfactants on the optical yield of the oxidation were studied and discussed.Generally,increasing the alkyl chain length both in sur- factants and in substrates enhances the optical yield,also the surfactant with hydroxy group at its appropriate position gives better enantioselectivity,suggesting the enzymic characteristics of the chiral micelle.展开更多
基金supported by the National Natural Science Foundation of China(22425108)the National Basic Research Program of China(2024YFA1509202)+2 种基金the Taishan Scholar Program at Shandong Province(tstp20231205)the Natural Science Foundation of Shandong Province(ZR2024QH454)the China Post-doctoral Science Foundation(2024M761873)。
文摘Oxidation is a fundamental reaction in organic chemistry and represents a unique strategy to convert starting materials with low oxidation states to new compounds with high oxidation states.Asymmetric oxidation is regarded as the most straightforward protocol to prepare chiral oxides with high oxidation states and has played a crucial role in the fields of organic synthesis,material science and the pharmaceutical industry.However,previous studies typically focused on several specific substrates,such as alkenes,alcohols,and ketones,which have been well summarized in many reviews.Exploration of new substrate categories and reaction patterns remains a major challenge in this field.During the last decade,considerable progress has been made in non-enzymatic catalyzed asymmetric oxidations of C(sp^(3))-H bonds and heteroatoms.These advancements have facilitated the creation of diverse chiral molecules exhibiting excellent chemoselectivity and stereoselectivity.In this review,we summarize the progress in catalytic asymmetric oxidation of C(sp^(3))-H bonds and heteroatoms during the past decade,which would provide insights into challenging issues and enable future development.
文摘A variety of phenyl alkyl sulfides were oxidized enantioselectively with NaIO_4 in chiral micellar systems formed from eight chiral surfactants,to give optical active sulfoxides.The enantiomer excesses ranged from 1.6 to 15.0%.To understand the mechanistic detail of this asymmetric oxi- dation in chiral micelle,the effects of structure both in substrates and surfactants on the optical yield of the oxidation were studied and discussed.Generally,increasing the alkyl chain length both in sur- factants and in substrates enhances the optical yield,also the surfactant with hydroxy group at its appropriate position gives better enantioselectivity,suggesting the enzymic characteristics of the chiral micelle.
