We developed a novel Pd-catalyzed[4+4]cycloaddition of(benzo)furan-derived azadienes with homo-TMM all-carbon 1,4-dipoles in situ generated fromα-allyl malonate derivatives,affording an array of benzofuro[3,2-b]azoci...We developed a novel Pd-catalyzed[4+4]cycloaddition of(benzo)furan-derived azadienes with homo-TMM all-carbon 1,4-dipoles in situ generated fromα-allyl malonate derivatives,affording an array of benzofuro[3,2-b]azocines and furo[3,2-b]azocines with good to excellent yields(up to 96%)and exclusive regioselectivities.This methodology featured mild reaction conditions and good functional group tolerance.The synthetic utility was demonstrated by a gram-scale reaction.Furthermore,the catalytic asymmetric[4+4]cycloaddition version has also been explored.展开更多
Palladium-catalyzed allylic alkylation enabled by ketone umpolung via Pudovik addition/[1,2]-phospha-Brook rearrangement with phosphites has been developed.The protocol offers a straightforward method for the synthesi...Palladium-catalyzed allylic alkylation enabled by ketone umpolung via Pudovik addition/[1,2]-phospha-Brook rearrangement with phosphites has been developed.The protocol offers a straightforward method for the synthesis of potentially bioactive homoallylic alcohol phosphonates in an efficient and economical way.This cascade reaction proceeds under mild conditions with excellent functional group compatibility.Furthermore,the catalytic asymmetric version has also been explored.展开更多
Transition-metal-catalyzed C–H bond functionalization has attracted tremendous attention as an increasingly important protocol for the construction of C–C and C–X bonds.In particular,C–H bond functionalization ass...Transition-metal-catalyzed C–H bond functionalization has attracted tremendous attention as an increasingly important protocol for the construction of C–C and C–X bonds.In particular,C–H bond functionalization assisted by the phosphorus-containing directing groups has made significant progress in the past few years.A series of valuable phosphorous compounds,especially phosphine ligands have been provided conveniently.This review comprehensively describes recent advances in transition-metal-catalyzed C–H bond functionalization assisted by the phosphorus-containing directing groups,highlights its potential applications in organic synthesis,and gives some insights into future advances.展开更多
of main observation and conclusion A palladium-catalyzed asymmetric[4+3]cycloaddition of trimethylenemethanes and indoline-derived aza-dienes has been developed.The potential[3+2]side pathway was completely suppressed...of main observation and conclusion A palladium-catalyzed asymmetric[4+3]cycloaddition of trimethylenemethanes and indoline-derived aza-dienes has been developed.The potential[3+2]side pathway was completely suppressed in the process.This protocol provides an efficient access to azepino[2,3-b]indoles bearing two vicinal stereocenters in generally excellent diastereo-and enantioselectivities(up to>20:1 dr,99% ee).展开更多
基金We are grateful for financial support from National Key Research and Development Program of China(2021YFA0804900)the NSFC(22171082,21971062)+1 种基金the Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang(No.2022R01007)Shanghai Frontiers Science Center of Optogenetic Techniques for Cell Metabolism.
文摘We developed a novel Pd-catalyzed[4+4]cycloaddition of(benzo)furan-derived azadienes with homo-TMM all-carbon 1,4-dipoles in situ generated fromα-allyl malonate derivatives,affording an array of benzofuro[3,2-b]azocines and furo[3,2-b]azocines with good to excellent yields(up to 96%)and exclusive regioselectivities.This methodology featured mild reaction conditions and good functional group tolerance.The synthetic utility was demonstrated by a gram-scale reaction.Furthermore,the catalytic asymmetric[4+4]cycloaddition version has also been explored.
基金supported by the National Key Research and Development Program of China(2021YFA0804900)the Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang(2022R01007)Shanghai Frontiers Science Center of Optogenetic Techniques for Cell Metabolism。
文摘Palladium-catalyzed allylic alkylation enabled by ketone umpolung via Pudovik addition/[1,2]-phospha-Brook rearrangement with phosphites has been developed.The protocol offers a straightforward method for the synthesis of potentially bioactive homoallylic alcohol phosphonates in an efficient and economical way.This cascade reaction proceeds under mild conditions with excellent functional group compatibility.Furthermore,the catalytic asymmetric version has also been explored.
基金supported by the Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang(No.2022R01007)the National Natural Science Foundation of China(Nos.21971062 and 22171082.)the Start-up Research Grant from Zhejiang Normal University.
文摘Transition-metal-catalyzed C–H bond functionalization has attracted tremendous attention as an increasingly important protocol for the construction of C–C and C–X bonds.In particular,C–H bond functionalization assisted by the phosphorus-containing directing groups has made significant progress in the past few years.A series of valuable phosphorous compounds,especially phosphine ligands have been provided conveniently.This review comprehensively describes recent advances in transition-metal-catalyzed C–H bond functionalization assisted by the phosphorus-containing directing groups,highlights its potential applications in organic synthesis,and gives some insights into future advances.
基金This work is supported by the National Natural Science Foundation of China(Nos.21772038,21971062,and 21901072)Shanghai Sailing Program(No.18YF140560).
文摘of main observation and conclusion A palladium-catalyzed asymmetric[4+3]cycloaddition of trimethylenemethanes and indoline-derived aza-dienes has been developed.The potential[3+2]side pathway was completely suppressed in the process.This protocol provides an efficient access to azepino[2,3-b]indoles bearing two vicinal stereocenters in generally excellent diastereo-and enantioselectivities(up to>20:1 dr,99% ee).
