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 chiral phosphoric acid catalyzed enantioselective[2+2] cycloaddition of alkynylindols or alkynylnaphthols with quinones is disclosed.A class of functionalized cyclobutenes with excellent yields,diastereo-and enantio...A chiral phosphoric acid catalyzed enantioselective[2+2] cycloaddition of alkynylindols or alkynylnaphthols with quinones is disclosed.A class of functionalized cyclobutenes with excellent yields,diastereo-and enantioselectivities were prepared under mild reaction conditions(70 examples,up to 99%yield,99%ee,all>50:1 dr).Mechanistic studies revealed that a dearomatization of indole or naphthol occurred to initiate the cycloaddition,followed by an intramolecular Michael addition with in situ generated allene-iminium or vinylidene-quinone methide intermediate.The competitive[2+3] cycloaddition was prevented in this catalytic system.An interesting central to axial chirality conversion via a rearrangement process was realized during transformation of the product.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.
基金supported by the National Natural Science Foundation of China(NSFC 21672170)the Natural Science Basic Research Plan in Shaanxi Province of China(2021JZ-40)Shaanxi Fundamental Science Research Project for Chemistry&Biology(22JHQ007)。
文摘A chiral phosphoric acid catalyzed enantioselective[2+2] cycloaddition of alkynylindols or alkynylnaphthols with quinones is disclosed.A class of functionalized cyclobutenes with excellent yields,diastereo-and enantioselectivities were prepared under mild reaction conditions(70 examples,up to 99%yield,99%ee,all>50:1 dr).Mechanistic studies revealed that a dearomatization of indole or naphthol occurred to initiate the cycloaddition,followed by an intramolecular Michael addition with in situ generated allene-iminium or vinylidene-quinone methide intermediate.The competitive[2+3] cycloaddition was prevented in this catalytic system.An interesting central to axial chirality conversion via a rearrangement process was realized during transformation of the product.
