Dearomative carboxylation of aromatic compounds with carbon dioxide(CO_(2))could be utilized for the synthesis of cyclic carboxylative frameworks.The dearomative carboxylation exhibits advantages such as reconstitutio...Dearomative carboxylation of aromatic compounds with carbon dioxide(CO_(2))could be utilized for the synthesis of cyclic carboxylative frameworks.The dearomative carboxylation exhibits advantages such as reconstitution molecular spatial structure,environmental friendliness,mild conditions,high yield,and high selectivity,and is of significant importance in pharmaceutical synthesis and natural product chemistry.The recent advancements in the dearomative carboxylation of aromatics with CO_(2) are summarized,including elucidation of the reaction characteristics and the scope of substrates via transition-metal catalysis,photoredox catalysis,and electropromoted chemistry.展开更多
Dearomative photocycloaddition of heteroarenes is an efficient method for replacing planar arenes with three-dimensional(3D)scaffolds,such as bicyclo[2.1.1]-hexane(BCH)containing heterocycles.Herein,we report intramol...Dearomative photocycloaddition of heteroarenes is an efficient method for replacing planar arenes with three-dimensional(3D)scaffolds,such as bicyclo[2.1.1]-hexane(BCH)containing heterocycles.Herein,we report intramolecular dearomative[2π+2σ]photocycloadditions of bicyclo[1.1.0]butanes(BCBs)with(benzo)furans and(benzo)thiophenes.These photocycloadditions are initiated through an energy transfer pathway(EnT)or single electron transfer pathway(SET),efficiently yielding unique BCHpyrrolidinone-fused heterocyclic scaffolds.Moreover,the synthetic utility of this photochemical reaction was demonstrated on the basis of large-scale synthesis and diversified transformations.Mechanistic investigations,in conjunction with density functional theory(DFT)calculations,were taken to support the proposed reaction mechanisms.展开更多
Indole-derived radical cations, open-shell reactive species, display distinctive dual reactivity due to the carbon-centered radical and more electrophilic carbocation, which frequently appear in a variety of single el...Indole-derived radical cations, open-shell reactive species, display distinctive dual reactivity due to the carbon-centered radical and more electrophilic carbocation, which frequently appear in a variety of single electron oxidation reactions for synthesizing structurally diverse functionalized indoles and indolines. Electrocatalysis is considered as a synthetically attractive and environmentally friendly alternative for driving the single electron oxidation of indoles. Remarkable achievements in electrocatalytic indolederived radical cation-mediated indole functionalization have been realized so far. This review comprehensively summarizes the recent progresses in the applications of electrocatalytic indole radical cations,including C(sp~2)–H functionalization, dearomative 2,3-difunctionalization, and ring-opening reaction, emphasizing the vital single electron oxidation steps of indoles, the substrates scope and limitations, and the reaction mechanisms.展开更多
The conjugate addition of in-situ generated(aza-)quinone methides(QMs)and indole imine methides(IIMs)emerged as a powerful protocol to access densely functionalized benzenes and indoles.Hydroxybenzyl alcohols,aminoben...The conjugate addition of in-situ generated(aza-)quinone methides(QMs)and indole imine methides(IIMs)emerged as a powerful protocol to access densely functionalized benzenes and indoles.Hydroxybenzyl alcohols,aminobenzhydryl alcohols,and varied indolylmethanols served as most effective precursors for the in-situ generation of such reactive species under acid conditions.The relevant propargylic alcohol has proven to be an elegant precursor to generate the propargylic-QMs and-IIMs via the acid promoted dehydration process,thus enabling diverse challenging remote activation to proceed conjugate1,6-and 1,8-additions.Moreover,the heteroarene has proven to be workable to transfer the LUMO of the p-QMs and 2-IIMs,thus inducing the remote nucleophilic dearomative additions.The conjugate additions of(aza-)p-QMs and varied IIMs has made significant contribution in the field of remote activation chemistry in past decade.This review summarizes the latest advances of the remote conjugate additions of the in-situ generated QMs and IIMs.展开更多
A concise synthetic route leading to highly functional erythrina alkaloid skeletons has been developed.The key process is an oxidative carbon-carbon coupling followed by a conjugated addition.Based on this new strateg...A concise synthetic route leading to highly functional erythrina alkaloid skeletons has been developed.The key process is an oxidative carbon-carbon coupling followed by a conjugated addition.Based on this new strategy,a formal synthesis of demethoxyerythratidinone was completed in only 6 steps from 4-aminophenol.展开更多
文摘Dearomative carboxylation of aromatic compounds with carbon dioxide(CO_(2))could be utilized for the synthesis of cyclic carboxylative frameworks.The dearomative carboxylation exhibits advantages such as reconstitution molecular spatial structure,environmental friendliness,mild conditions,high yield,and high selectivity,and is of significant importance in pharmaceutical synthesis and natural product chemistry.The recent advancements in the dearomative carboxylation of aromatics with CO_(2) are summarized,including elucidation of the reaction characteristics and the scope of substrates via transition-metal catalysis,photoredox catalysis,and electropromoted chemistry.
基金supported by the National Key R&D Program of China(2022YFC2303100)the National Natural Science Foundation of China(22305261,21372250,21121062,21302203,20732008,21772037,21772226,21861132014,91956115,22171078)+1 种基金the Shanghai Municipal Science and Technology Major Project(2018SHZDZX03)the Fundamental Research Funds for the Central Universities(222201717003)。
文摘Dearomative photocycloaddition of heteroarenes is an efficient method for replacing planar arenes with three-dimensional(3D)scaffolds,such as bicyclo[2.1.1]-hexane(BCH)containing heterocycles.Herein,we report intramolecular dearomative[2π+2σ]photocycloadditions of bicyclo[1.1.0]butanes(BCBs)with(benzo)furans and(benzo)thiophenes.These photocycloadditions are initiated through an energy transfer pathway(EnT)or single electron transfer pathway(SET),efficiently yielding unique BCHpyrrolidinone-fused heterocyclic scaffolds.Moreover,the synthetic utility of this photochemical reaction was demonstrated on the basis of large-scale synthesis and diversified transformations.Mechanistic investigations,in conjunction with density functional theory(DFT)calculations,were taken to support the proposed reaction mechanisms.
基金the National Natural Science Foundation of China (No.22261019)the Jiangxi Provincial Natural Science Foundation (No.20224BAB213004)+1 种基金the Education Department of Jiangxi Province(Nos.GJJ211134 and GJJ211137)the PhD start-up fund of Jiangxi Science&Technology Normal University (No.2021BSQD32) for financial support。
文摘Indole-derived radical cations, open-shell reactive species, display distinctive dual reactivity due to the carbon-centered radical and more electrophilic carbocation, which frequently appear in a variety of single electron oxidation reactions for synthesizing structurally diverse functionalized indoles and indolines. Electrocatalysis is considered as a synthetically attractive and environmentally friendly alternative for driving the single electron oxidation of indoles. Remarkable achievements in electrocatalytic indolederived radical cation-mediated indole functionalization have been realized so far. This review comprehensively summarizes the recent progresses in the applications of electrocatalytic indole radical cations,including C(sp~2)–H functionalization, dearomative 2,3-difunctionalization, and ring-opening reaction, emphasizing the vital single electron oxidation steps of indoles, the substrates scope and limitations, and the reaction mechanisms.
基金the financial support from the National Natural Science Foundation of China(No.22001216)the Chemical Synthesis and Pollution Control Key Laboratory of Sichuan Province(No.CSPC202315)+2 种基金the Science and Technology Department of Sichuan Province,China(No.2022NSFSC1203)the Higher Education Institution Key Research Project Plan of Henan Province(No.24B150031)the Program for Youth Backbone Teacher Training in University of Henan Province(No.2021GGJS163)。
文摘The conjugate addition of in-situ generated(aza-)quinone methides(QMs)and indole imine methides(IIMs)emerged as a powerful protocol to access densely functionalized benzenes and indoles.Hydroxybenzyl alcohols,aminobenzhydryl alcohols,and varied indolylmethanols served as most effective precursors for the in-situ generation of such reactive species under acid conditions.The relevant propargylic alcohol has proven to be an elegant precursor to generate the propargylic-QMs and-IIMs via the acid promoted dehydration process,thus enabling diverse challenging remote activation to proceed conjugate1,6-and 1,8-additions.Moreover,the heteroarene has proven to be workable to transfer the LUMO of the p-QMs and 2-IIMs,thus inducing the remote nucleophilic dearomative additions.The conjugate additions of(aza-)p-QMs and varied IIMs has made significant contribution in the field of remote activation chemistry in past decade.This review summarizes the latest advances of the remote conjugate additions of the in-situ generated QMs and IIMs.
基金This work was supported by grants(20925205,21062026,2010GA014 and 2009CB522300) from National Natural Science Foundation of China,Yunnan Province and National Basic Research Program of China(973 Program).
文摘A concise synthetic route leading to highly functional erythrina alkaloid skeletons has been developed.The key process is an oxidative carbon-carbon coupling followed by a conjugated addition.Based on this new strategy,a formal synthesis of demethoxyerythratidinone was completed in only 6 steps from 4-aminophenol.
