Spiro heterocycles frequently occur in bioactive molecules. In the pursuit of neonicotinoids with spiro hererocycles, three types of novel neonicotinoids with spirobenzofuranone, spirooxindole or spiroacenaphythylenon...Spiro heterocycles frequently occur in bioactive molecules. In the pursuit of neonicotinoids with spiro hererocycles, three types of novel neonicotinoids with spirobenzofuranone, spirooxindole or spiroacenaphythylenone framework were designed and synthesized. Insecticidal evaluation showed that some of spirobenzofuranone containing neonicotinoids exhibited moderate activity against cowpea aphid, armyworm or brown planthopper.展开更多
Transition metal-catalyzed asymmetric allylic substitution reaction has been recognized as a powerful method to enable cross-coupling reactions for the efficient preparation of chiral molecules.Palladiumπ-allyl speci...Transition metal-catalyzed asymmetric allylic substitution reaction has been recognized as a powerful method to enable cross-coupling reactions for the efficient preparation of chiral molecules.Palladiumπ-allyl species,generally serving as key electrophilic partners,have yet to be explored as amphiphilic electro-/nucleophilic partners.Herein,we developed such a novel reaction mode via copper/palladium cocatalyzed cascade allylic alkylation/aza-Prins cyclization of cyclic aldimine esters with 2-indolyl allyl carbonates.A large number of valuable chiral spiroindolylpiperidine-γ-butyrolactone derivatives were obtained in decent yields with excellent diastereo-/enantioselective control(up to 90%yield,>20:1 dr and 99%ee).Gram-scale reaction and several transformations were exemplified to illustrate the potential for synthetic applications.This cascade protocol features step economy,and high control levels with chemo-/diastereo-/enantioselectivities.Additionally,biological evaluation against five types of cancer cell lines revealed potent anticancer capabilities,indicating that these compounds have potential as anticancer drug candidates.Moreover,density functional theory computational studies unveiled the mechanism of asymmetric allylic alkylation via cooperative copper/palladium catalysis,in which the stereochemistry was regulated by an ensemble of dispersion interactions and steric effects.The ensuing acid-enabled aza-Prins cyclization provided the final polycyclic product,and structure-activity analysis revealed the origins of stereoselectivity and chemoselectivity.展开更多
基金financial supported by National Basic Research Program of China(973 Program,No.2010CB126100)National High Technology Research Development Program of China(863 Program,No.2011AA10A207)+4 种基金Key Projects in the National Science & Technology Pillar Program(No.2011BAE06B05)National Natural Science Foundation of China(No.21372079)Shanghai Education Committee(No.12ZZ057)the Fundamental Research Funds for the Central Universitiespartly supported by Australia DC Foundation
文摘Spiro heterocycles frequently occur in bioactive molecules. In the pursuit of neonicotinoids with spiro hererocycles, three types of novel neonicotinoids with spirobenzofuranone, spirooxindole or spiroacenaphythylenone framework were designed and synthesized. Insecticidal evaluation showed that some of spirobenzofuranone containing neonicotinoids exhibited moderate activity against cowpea aphid, armyworm or brown planthopper.
基金supported by the National Key R&D Program of China(grant no.2023YFA1506700)National Natural Science Foundation of China(grant nos.22071186,22071187,22101216,22073067,22271226,and 22371216)+2 种基金National Youth Talent Support Program,Hubei Province Natural Science Foundation(grant no.2021CFA069)China Postdoctoral Science Foundation(grant no.2021M702514)Fundamental Research Funds for the Central Universities(grant nos.2042022kf1180 and 2042022kf1040)。
文摘Transition metal-catalyzed asymmetric allylic substitution reaction has been recognized as a powerful method to enable cross-coupling reactions for the efficient preparation of chiral molecules.Palladiumπ-allyl species,generally serving as key electrophilic partners,have yet to be explored as amphiphilic electro-/nucleophilic partners.Herein,we developed such a novel reaction mode via copper/palladium cocatalyzed cascade allylic alkylation/aza-Prins cyclization of cyclic aldimine esters with 2-indolyl allyl carbonates.A large number of valuable chiral spiroindolylpiperidine-γ-butyrolactone derivatives were obtained in decent yields with excellent diastereo-/enantioselective control(up to 90%yield,>20:1 dr and 99%ee).Gram-scale reaction and several transformations were exemplified to illustrate the potential for synthetic applications.This cascade protocol features step economy,and high control levels with chemo-/diastereo-/enantioselectivities.Additionally,biological evaluation against five types of cancer cell lines revealed potent anticancer capabilities,indicating that these compounds have potential as anticancer drug candidates.Moreover,density functional theory computational studies unveiled the mechanism of asymmetric allylic alkylation via cooperative copper/palladium catalysis,in which the stereochemistry was regulated by an ensemble of dispersion interactions and steric effects.The ensuing acid-enabled aza-Prins cyclization provided the final polycyclic product,and structure-activity analysis revealed the origins of stereoselectivity and chemoselectivity.
