A metal-free,green,and sustainable functionalization of unactivated alkyl sp^(3) C—H bonds is reported using iodine(III)as a feasible dehydrogenation agent under visible light or KBr,and alkyl chlorides,bromides,alco...A metal-free,green,and sustainable functionalization of unactivated alkyl sp^(3) C—H bonds is reported using iodine(III)as a feasible dehydrogenation agent under visible light or KBr,and alkyl chlorides,bromides,alcohols,and ketones could be constructed by addition of different coupling reagents.Cheap and safe iodobenzene diacetate was used to form a radical to activate the alkyl sp^(3) C—H bond in a highly efficient manner,which can construct different alkylation products by adding corresponding coupling reagents.展开更多
A radical decarboxylative C(sp^(3))–C(sp^(3))cross-coupling of NHPI esters and cyclopropanols was developed by combining photocatalysis and copper catalysis,which presents the efficient access toβ-benzyl ketones in ...A radical decarboxylative C(sp^(3))–C(sp^(3))cross-coupling of NHPI esters and cyclopropanols was developed by combining photocatalysis and copper catalysis,which presents the efficient access toβ-benzyl ketones in excellent yields.Terpyridin-4′-one used as the ligand is vital for the reaction,which could facilitate the capture of benzylic radicals by alkyl-copper species generated from copper-catalyzed ring-opening of cyclopropanols.The reaction exhibited broad substrate scope and wide functional group compatibility,providing an alternative approach for C(sp^(3))–C(sp^(3))bond formation.展开更多
Thioether skeletons are widely present in drugs,natural products,functional materials,and life science.In the past decade,the selective C–H functionalization of thioethers has been extensively studied to construct no...Thioether skeletons are widely present in drugs,natural products,functional materials,and life science.In the past decade,the selective C–H functionalization of thioethers has been extensively studied to construct novel thioether derivatives.This mini-review systematically introduces the recent advances in the field of the directα-C(sp^(3))-H functionalization of thioethers.展开更多
Oximes derivatives have been vastly used in organic synthesis. In this review, C(sp^(3))-H bond functionalization of oximes derivatives via iminyl radical induced 1,5-hydrogen atom transfer was discussed. According to...Oximes derivatives have been vastly used in organic synthesis. In this review, C(sp^(3))-H bond functionalization of oximes derivatives via iminyl radical induced 1,5-hydrogen atom transfer was discussed. According to the different type of products, this review was divided into three parts: (1) C(sp^(3))-H bond functionalization for C-C bond formation. (2) C(sp^(3))-H bond functionalization for C-N bond formation. (3) C(sp^(3))-H bond functionalization for C-S, C-F bond formation.展开更多
In recent years,the transition metal-free sulfenylation of C-H bond for C-S formation has been rapidly advanced and has become an eco-friendly synthetic tool for pharmacists and organic chemists.Various natural or bio...In recent years,the transition metal-free sulfenylation of C-H bond for C-S formation has been rapidly advanced and has become an eco-friendly synthetic tool for pharmacists and organic chemists.Various natural or bioactive molecules such as(hetero)arenes,olefins,carbonyl compounds,alkanes,have been employed for sulfenylating reactions.This review will focus on the recent five-year advances in C-S bond formation via direct sulfenylation of C(sp^3)-H bonds under metal-free conditions and elaborate their mechanisms from a new perspective.展开更多
Organofluorine compounds are widely used in the realm of drug discovery and material science.Herein,we developed palladium catalyzed intermolecular aminofluorination and oxy-aminofluorination of gem‑difluoroalkenes wi...Organofluorine compounds are widely used in the realm of drug discovery and material science.Herein,we developed palladium catalyzed intermolecular aminofluorination and oxy-aminofluorination of gem‑difluoroalkenes with N-fluorobenzenesulfonimide(NFSI),in which NFSI was used as the nitrogen source and oxidant.The reaction provides an efficient and straightforward synthesis route of a series ofα-trifluoromethyl benzylic amines.Notably,three/four components oxy-aminofluorination processes were realized to giveα-trifluoromethyl benzylic ether with a terminal amino group,which proceed through C(sp^(3))-O bond cleavage of easily available ether and simultaneous introduced a fluorine,an amino and an oxy substituent in one pot with excellent regioselectivity.The divergent reactivity not only included the incorporation of one ether molecular,but also much more challenged two ether insertion with excellent selectivity through succession C(sp^(3))-O bonds cleavage.This protocol allows for concise synthesis of high value amines with fluoroalkyl-substituents and selectively transformation of easily available ethers by high-valent palladium catalysis.展开更多
Zinc-promoted umpolung thiolation of alkyl electrophiles with masked sulfur transfer reagents in the absence of nickel or copper catalysis is described. This protocol proceeds via a SET process of Zn to electrophilic ...Zinc-promoted umpolung thiolation of alkyl electrophiles with masked sulfur transfer reagents in the absence of nickel or copper catalysis is described. This protocol proceeds via a SET process of Zn to electrophilic sulfur reagent followed by insertion of Zn into disulfide and nucleophilic thiolation, providing straightforward access to a wide range of alkyl sulfides with broad substrate scope. A neutral TMEDA-ligated four-coordinated zinc thiolate with tetrahedra geometry was synthesized, isolated and fully characterized by NMR, IR and X-ray analysis. More importantly, the chemical reactivity of this active intermediate has been investigated, enabling the construction of C-Se, C-Te, Sb-S and Bi-S bonds to prepare valuable sulfur-containing molecules and beyond.展开更多
基金supported the Natural Science Foundation of Higher Education Institutions in Anhui Province(2022AH030133,2022AH051340)National Natural Science Foundation of China(22231003,22271008)+6 种基金Shenzhen Science and Technology Program(Grant No.KQTD20190929174023858)Shenzhen Science and Technology Innovation Committee(GXWD20201231165807007-20200812100115001)Shenzhen-Hong Kong Institute of Brain Science-Shenzhen Fundamental Research Institutions(2023SHIBS0004)Horizontal Cooperation Project of Fuyang Municipal Government(SXHZ202201)Key Projects of the Support Program for Outstanding Young Talents in Anhui Province Colleges and Universities(gxyqZD2020030)Yifan Pharmaceutical Co.,Ltd.(HX2019033)Innovative Drug Design&Development Collaborative Team(TDYY2021009).
文摘A metal-free,green,and sustainable functionalization of unactivated alkyl sp^(3) C—H bonds is reported using iodine(III)as a feasible dehydrogenation agent under visible light or KBr,and alkyl chlorides,bromides,alcohols,and ketones could be constructed by addition of different coupling reagents.Cheap and safe iodobenzene diacetate was used to form a radical to activate the alkyl sp^(3) C—H bond in a highly efficient manner,which can construct different alkylation products by adding corresponding coupling reagents.
基金supported by the National Key R&D Program of China(2021YFA1500100)the National Natural Science Foundation of China(91956202,92256301,21821002,21971255)+1 种基金the Science and Technology Commission of Shanghai Municipality(20JC1417000,21520780100)the International Partnership Program(121731KYSB20190016)of the Chinese Academy of Sciences。
文摘A radical decarboxylative C(sp^(3))–C(sp^(3))cross-coupling of NHPI esters and cyclopropanols was developed by combining photocatalysis and copper catalysis,which presents the efficient access toβ-benzyl ketones in excellent yields.Terpyridin-4′-one used as the ligand is vital for the reaction,which could facilitate the capture of benzylic radicals by alkyl-copper species generated from copper-catalyzed ring-opening of cyclopropanols.The reaction exhibited broad substrate scope and wide functional group compatibility,providing an alternative approach for C(sp^(3))–C(sp^(3))bond formation.
基金support from the National Natural Science Foundation of China(NSFC,No.21702019)and Advanced Catalysis and Green Manufacturing Collaborative Innovation Center,Changzhou UniversityHaibo Ge,Mazen Elsaid and Chong Liu acknowledge NSF(No.CHE-2029932),Robert A.Welch Foundation(No.D-2034-20200401),and the Texas Tech University for financial support.
文摘Thioether skeletons are widely present in drugs,natural products,functional materials,and life science.In the past decade,the selective C–H functionalization of thioethers has been extensively studied to construct novel thioether derivatives.This mini-review systematically introduces the recent advances in the field of the directα-C(sp^(3))-H functionalization of thioethers.
基金supported by the National Natural Science Foundation of China (Nos. 21772107, 21901010)Shandong Province Key Research and Development Plan (No. 2019GSF108017)。
文摘Oximes derivatives have been vastly used in organic synthesis. In this review, C(sp^(3))-H bond functionalization of oximes derivatives via iminyl radical induced 1,5-hydrogen atom transfer was discussed. According to the different type of products, this review was divided into three parts: (1) C(sp^(3))-H bond functionalization for C-C bond formation. (2) C(sp^(3))-H bond functionalization for C-N bond formation. (3) C(sp^(3))-H bond functionalization for C-S, C-F bond formation.
基金financial support from the Young Scholars Research Fund of Yantai University (No.HY19B06)
文摘In recent years,the transition metal-free sulfenylation of C-H bond for C-S formation has been rapidly advanced and has become an eco-friendly synthetic tool for pharmacists and organic chemists.Various natural or bioactive molecules such as(hetero)arenes,olefins,carbonyl compounds,alkanes,have been employed for sulfenylating reactions.This review will focus on the recent five-year advances in C-S bond formation via direct sulfenylation of C(sp^3)-H bonds under metal-free conditions and elaborate their mechanisms from a new perspective.
基金supported by the National Natural Science Foundation of China(Nos.82130103,U1804283,21801067)the Central Plains Scholars and Scientists Studio Fund(No.2018002)+2 种基金the Project funded by the Natural Science Foundation of Henan Province(Nos.202300410225,222102310562)Henan Postdoctoral Science Foundation(No.202103087)the financial support from Henan Key Laboratory of Organic Functional Molecules and Drug Innovation.
文摘Organofluorine compounds are widely used in the realm of drug discovery and material science.Herein,we developed palladium catalyzed intermolecular aminofluorination and oxy-aminofluorination of gem‑difluoroalkenes with N-fluorobenzenesulfonimide(NFSI),in which NFSI was used as the nitrogen source and oxidant.The reaction provides an efficient and straightforward synthesis route of a series ofα-trifluoromethyl benzylic amines.Notably,three/four components oxy-aminofluorination processes were realized to giveα-trifluoromethyl benzylic ether with a terminal amino group,which proceed through C(sp^(3))-O bond cleavage of easily available ether and simultaneous introduced a fluorine,an amino and an oxy substituent in one pot with excellent regioselectivity.The divergent reactivity not only included the incorporation of one ether molecular,but also much more challenged two ether insertion with excellent selectivity through succession C(sp^(3))-O bonds cleavage.This protocol allows for concise synthesis of high value amines with fluoroalkyl-substituents and selectively transformation of easily available ethers by high-valent palladium catalysis.
基金the National Science Foundation of China(22001051)Zhejiang Provincial Natural Science Foundation of China(LY23B020002)for financial supportfunding from the STU Scientific Research Foundation for Talents(NTF20022)。
文摘Zinc-promoted umpolung thiolation of alkyl electrophiles with masked sulfur transfer reagents in the absence of nickel or copper catalysis is described. This protocol proceeds via a SET process of Zn to electrophilic sulfur reagent followed by insertion of Zn into disulfide and nucleophilic thiolation, providing straightforward access to a wide range of alkyl sulfides with broad substrate scope. A neutral TMEDA-ligated four-coordinated zinc thiolate with tetrahedra geometry was synthesized, isolated and fully characterized by NMR, IR and X-ray analysis. More importantly, the chemical reactivity of this active intermediate has been investigated, enabling the construction of C-Se, C-Te, Sb-S and Bi-S bonds to prepare valuable sulfur-containing molecules and beyond.
