期刊：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2024年146(28):18892–18898 ISSN：0002-7863
通讯作者：
Xiao, WJ
作者机构：
[Lu, Liang-Qiu; Cheng, Ying; Yuan, Bao-Ru; Luo, Jia-Long; Xiao, Wen-Jing; Xiao, WJ; He, Xiang-Kui] Cent China Normal Univ, Coll Chem, Engn Res Ctr Photoenergy Utilizat Pollut Control &, Minist Educ, Wuhan 430079, Peoples R China.;[Lu, Liang-Qiu; Xiao, Wen-Jing; Xiao, WJ] Wuhan Inst Photochem & Technol, Wuhan 430080, Peoples R China.;[Lu, Liang-Qiu] Henan Normal Univ, Sch Chem & Chem Engn, Xinxiang 453007, Henan, Peoples R China.;[Xiao, Wen-Jing; Xiao, WJ] Lanzhou Univ, State Key Lab Appl Organ Chem, Lanzhou 730000, Gansu, Peoples R China.
通讯机构：
[Xiao, WJ ] C;Cent China Normal Univ, Coll Chem, Engn Res Ctr Photoenergy Utilizat Pollut Control &, Minist Educ, Wuhan 430079, Peoples R China.;Wuhan Inst Photochem & Technol, Wuhan 430080, Peoples R China.;Lanzhou Univ, State Key Lab Appl Organ Chem, Lanzhou 730000, Gansu, Peoples R China.
摘要：
Herein, we designed a reaction for the desymmetrization-addition of cyclopropenes to imines by leveraging the synergy between photoredox and asymmetric cobalt catalysis. This protocol facilitated the synthesis of a series of chiral functionalized cyclopropanes with high yield, enantioselectivity, and diastereoselectivity (44 examples, up to 93% yield and >99% ee). A possible reaction mechanism involving cyclopropene desymmetrization by Co-H species and imine addition by Co-alkyl species was proposed. This study provides a novel route to important chiral cyclopropanes and extends the frontier of asymmetric metallaphotoredox catalysis.
摘要：
Photoinduced enantioselective strategies provide an efficient way to access chiral all-carbon quaternary stereocenters. Compared with the well-developed metal-catalyzed asymmetric conjugate addition of organometallic reagents to enones, the construction of chiral all-carbon quaternary stereocenters through a radical process still remains challenging, especially for the acyclic enones due to their enhanced conformational mobility. Herein, we disclose a photoinduced cobalt-catalyzed asymmetric radical coupling of alpha,beta-unsaturated 2-acyl imidazoles and alpha-silylamines to give beta,beta-disubstituted gamma-amino acid derivatives with acyclic quaternary carbon stereocenters. The facile protocol shows good functional group tolerance and a broad substrate scope. The corresponding chiral products were obtained in generally good yields (up to 96%) with high enantioselectivities (up to 99:1 e.r.).
期刊：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2024年146(39):26622-26629 ISSN：0002-7863
通讯作者：
Zhang, Zhihan;Lu, LQ
作者机构：
[Lu, Liang-Qiu; Lu, LQ; Zhang, Zhihan; Xiao, Meng; Xiao, Wen-Jing; Zhao, Jin-Pu; Shi, Bin] Cent China Normal Univ, Coll Chem, Engn Res Ctr Photoenergy Utilizat Pollut Control &, Minist Educ, Wuhan 430079, Peoples R China.;[Xiao, Wen-Jing] Wuhan Inst Photochem & Technol, Wuhan 430082, Hubei, Peoples R China.;[Lu, Liang-Qiu; Lu, LQ] Henan Normal Univ, Sch Chem & Chem Engn, Xinxiang 453007, Peoples R China.;[Lu, Liang-Qiu; Lu, LQ] Chinese Acad Sci, Lanzhou Inst Chem Phys LICP, State Key Lab Oxo Synth & Select Oxidat, Lanzhou 730000, Peoples R China.
通讯机构：
[Lu, LQ ; Zhang, ZH] C;Cent China Normal Univ, Coll Chem, Engn Res Ctr Photoenergy Utilizat Pollut Control &, Minist Educ, Wuhan 430079, Peoples R China.;Henan Normal Univ, Sch Chem & Chem Engn, Xinxiang 453007, Peoples R China.;Chinese Acad Sci, Lanzhou Inst Chem Phys LICP, State Key Lab Oxo Synth & Select Oxidat, Lanzhou 730000, Peoples R China.
摘要：
A Pd-catalyzed asymmetric higher-order dipolar cycloaddition between allenyl carbonates and azadienes is achieved by exploiting novel alkylidene-π-allyl-Pd dipoles. This research provides a modular platform for the synthesis of challenging chiral endocyclic allenes bearing a medium-sized heterocyclic motif and a centrally chiral stereocenter in good yields with high enantio- and diastereoselectivities (29 examples, up to 97% yield, 97:3 er and >19:1 dr). Experimental and computational studies elucidate the possible reaction mechanism and the observed stereochemical results. Based on the mechanistic understanding, a new π-propargyl-Pd dipole was designed to further extend the success of the higher order dipolar cycloaddition strategy to the synthesis of 10-membered endocyclic alkynes from propargyl carbonates and azadienes (13 examples, up to 98% yield and 94.5:5.5 er).
作者机构：
[Peng Chen; Mao-Mao Zhang] Engineering Research Center of Photoenergy Utilization for Pollution Control and Carbon Reduction, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan, China;Wuhan Institute of Photochemistry and Technology, Wuhan, China;State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of Sciences, Lanzhou, China;School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, China;[Wen-Jing Xiao] Engineering Research Center of Photoenergy Utilization for Pollution Control and Carbon Reduction, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan, China<&wdkj&>Wuhan Institute of Photochemistry and Technology, Wuhan, China
通讯机构：
[Liang-Qiu Lu] E;Engineering Research Center of Photoenergy Utilization for Pollution Control and Carbon Reduction, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan, China<&wdkj&>Wuhan Institute of Photochemistry and Technology, Wuhan, China<&wdkj&>State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of Sciences, Lanzhou, China<&wdkj&>School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, China
摘要：
<正>Chiral α-tertiary amines and related azacycles are commonly found in many natural products, pharmaceuticals and agrochemicals [1]. Copper-catalyzed asymmetric propargylic amination(APA) reactions have been established as a reliable method to access enantio-enriched propargylic amines,largely due to the seminal contribution of Nishibayashi et al.[2] and van Maarseveen et al. [3] in 2008.
摘要：
Isodesmic reactions, in which chemical bonds are redistributed between substrates and products, provide a general and powerful strategy for both biological and chemical synthesis. However, most isodesmic reactions involve either metathesis or functional-group transfer. Here, we serendipitously discovered a novel isodesmic reaction of indoles and anilines that proceeds intramolecularly under weakly acidic conditions. In this process, the five-membered ring of the indole motif is broken and a new indole motif is constructed on the aniline side, accompanied by the formation of a new aniline motif. Mechanistic studies revealed the pivotal role of sigma ->pi* hyperconjugation on the nitrogen atom of the indole motif in driving this unusual isodesmic reaction. Furthermore, we successfully synthesized a diverse series of polycyclic indole derivatives; among quinolines, potential antitumor agents were identified using cellular and in vivo experiments, thereby demonstrating the synthetic utility of the developed methodology. An unprecedented isodesmic reaction of indoles and anilines was developed in this work. The sigma ->pi* hyperconjugation between alkyl group and indole ring was identified as the driving force of this transformation through theoretical and experimental studies. The developed methodology was applied to obtain antitumor quindoline derivatives that exhibited substantial activity in both in vitro assays and in vivo models. image
作者机构：
[Xiao, Wen-Jing; Chen, Jia-Rong; Wang, Peng-Zi; Zhang, Zhihan] Engineering Research Center of Photoenergy Utilization for Pollution Control and Carbon Reduction, Ministry of Education;[Xiao, Wen-Jing; Chen, Jia-Rong; Wang, Peng-Zi; Zhang, Zhihan] College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei, 430079, China;[Jiang, Min] College of Materials, Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou, 310036, China;[Xiao, Wen-Jing; Chen, Jia-Rong] Wuhan Institute of Photochemistry and Technology, 7 North Bingang Road, Wuhan, Hubei, 430083, China
摘要：
Radical-involved arylative cross-coupling reactions have recently emerged as an attractive strategy to access valuable aryl-substituted motifs. However, there still exist several challenges such as limited scope of radical precursors/acceptors, and lack of general asymmetric catalytic systems, especially regarding the multicomponent variants. Herein, we reported a general copper-Box system for asymmetric three-component arylative radical cross-coupling of vinylarenes and 1,3-enynes, with oxime carbonates and aryl boronic acids. The reactions proceed under practical conditions in the absence or presence of visible-light irradiation, affording chiral 1,1-diarylalkanes, benzylic alkynes and allenes with good enantioselectivities. Mechanistic studies imply that the copper/Box complexes play a dual role in both radical generation and ensuing asymmetric cross-coupling. In the cases of 1,3-enynes, visible-light irradiation could improve the activity of copper/Box complex toward the initial radical generation, enabling better efficiency match between radical formation and cross-coupling.
摘要：
Organic molecules bearing chiral sulfur stereocenters exert a great impact on asymmetric catalysis and synthesis, chiral drugs, and chiral materials. Compared with acyclic ones, the catalytic asymmetric synthesis of thio-heterocycles has largely lagged behind due to the lack of efficient synthetic strategies. Here we establish the first modular platform to access chiral thio-oxazolidinones via Pd-catalyzed asymmetric [3+2] annulations of vinylethylene carbonates with sulfinylanilines. This protocol is featured by readily available starting materials, and high enantio- and diastereoselectivity. In particular, an unusual effect of a non-chiral supporting ligand on the diastereoselectivity was observed. Possible reaction mechanisms and stereocontrol models were proposed.
期刊：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2024年146(2):1410-1422 ISSN：0002-7863
通讯作者：
Xiao, Wen-Jing;Chen, JR
作者机构：
[Zhao, Ke; Qu, Wen-Yuan; Xiao, Wen-Jing; Chen, Jia-Rong; Mao, Zhi-Cheng; Zhang, Bin; Xiao, WJ; Li, Tian-Tian; Zhang, Zhihan; Chen, JR] Cent China Normal Univ, Coll Chem, Wuhan 430079, Hubei, Peoples R China.;[Jiang, Min] Hangzhou Normal Univ, Coll Mat Chem & Chem Engn, Hangzhou 310036, Peoples R China.;[Xiao, Wen-Jing; Chen, Jia-Rong; Xiao, WJ; Chen, JR] Wuhan Inst Photochem & Technol, Wuhan 430082, Hubei, Peoples R China.
通讯机构：
[Xiao, WJ; Chen, JR ] C;Cent China Normal Univ, Coll Chem, Wuhan 430079, Hubei, Peoples R China.;Wuhan Inst Photochem & Technol, Wuhan 430082, Hubei, Peoples R China.
摘要：
Alkene radical ions constitute an integral and unique class of reactive intermediates for the synthesis of valuable compounds because they have both unpaired spins and charge. However, relatively few synthetic applications of alkene radical anions have emerged due to a dearth of generally applicable and mild radical anion generation approaches. Precise control over the chemo- and stereoselectivity in alkene radical anion-mediated processes represents another long-standing challenge due to their high reactivity. To overcome these issues, here, we develop a new redox-neutral strategy that seamlessly merges photoredox and copper catalysis to enable the controlled generation of alkene radical anions and their orthogonal enantioselective cyanofunctionalization via distonic-like species. This new strategy enables highly regio-, chemo-, and enantioselective hydrocyanation, deuterocyanation, and cyanocarboxylation of alkenes without stoichiometric reductants or oxidants under visible light irradiation. This protocol provides a new blueprint for the exploration of the transformation potential of alkene radical anions.
摘要：
Highly efficient three‐component coupling of organic halides, sodium cyanate and amines or alcohols was achieved with a nickel/photoredox dual catalysis system. Significant N‐containing functional compounds, ureas and carbamates, were produced under green and sustainable conditions. Comprehensive Summary Ureas are widely used in drugs, materials and catalysts because of their diamide structure, which can form strong hydrogen bonds. Therefore, it is of great scientific significance to develop efficient and green methods for the synthesis of urea compounds, especially unsymmetrical ureas. Here, we have disclosed novel and highly efficient three‐component coupling reactions of organic halides, sodium cyanate and amines enabled by nickel/photoredox dual catalysis for the preparation of unsymmetrical ureas. The reaction features simple and safe operations, broad substrate scopes, and product diversities. It allows the facile synthesis of N‐aryl/vinyl ureas from readily available, user‐friendly feedstocks under mild conditions (27 examples, 36%—98% yields). In addition, this method is further derived to alcohols as nucleophiles to synthesize a series of carbamates (15 examples, 40%—95% yields). The mechanism experiment shows that the isocyanate produced by the coupling of halide and sodium cyanate may be the key intermediate in this reaction.
摘要：
An asymmetric cascade cyclization of enynamides and alpha-diazoketones to produce chiral bicyclic lactams bearing chiral all-carbon quaternary stereocenters is realized with up to 95% yield, 98% ee, and >19:1 dr. The combination of visible light photoactivation and the relay of gold and N-oxide catalysis in a cascade process enabled the facile generation and controlled assembly of two reactive intermediates, ketene and aza-o-quinone methide. Theoretical calculations revealed a stepwise [4 + 2] cycloaddition mechanism, with the stereochemistry controlled by the amide group of the catalyst. Remarkably, this study presents the first example of chiral N-oxides serving as catalysts for asymmetric ketene cycloaddition and illustrates how a cascade strategy could be a promising means to access significant chiral heterocyclic scaffolds.
摘要：
Radical-involved allylation reactions have emerged as a powerful platform for construction of carbon-carbon and carbonheteroatom bonds, facilitating the strategic incorporation of diverse allyl moieties. Nevertheless, this burgeoning field still faces ongoing challenges, including limitations of radical precursors and coupling partners, and difficulties in achieving enantiocontrol. Herein, we report for the first time a highly enantioselective radical allylation involving beta-keto esters with vinyl cyclopropanes utilizing a synergistic dual photoredox/nickel catalysis under visible light irradiation. The mild and redox-neutral catalytic protocol demonstrates an extensive substrate compatibility and good functional tolerance, providing access to enantioenriched beta-keto esters featuring quaternary alpha-stereocenter with good yields and high enantioselectivities. Preliminary mechanistic studies have uncovered that the success of the reaction hinges on the dual roles of nickel catalyst, including in situ formation of photoredox sensitive substrate/Ni complex and the ensuing asymmetric radical addition step.
摘要：
A visible‐light‐driven four‐component radical relay aminocarbonylation reaction of unactivated alkenes using 4CzIPN as an organic photocatalyst is developed, providing robust access to β‐fluoroalkyl amides with good yields and selectivity under metal‐free conditions. Importantly, this strategy also shows good compatibility with tertiary carbon radicals. Comprehensive Summary Catalytic four‐component radical carbonylation of unactivated alkenes has recently been recognized as a robust protocol for rapid construction of various structurally diverse carbonyl compounds. Given the significance of fluorine‐containing groups, this reaction class has been extensively applied to assembly of a variety of perfluoroalkyl carboxylic acid derivatives by transition metal catalysis. Herein, we report a visible‐light‐driven radical relay 1,2‐perfluoroalkylation aminocarbonylation of unactivated alkenes using CO gas as carbonyl source and 4CzIPN as organic photocatalyst. A wide range of alkenes and amines were well tolerated, providing the valuable β‐perfluoroalkylated amides with generally good yields and high chemoselectivity.
摘要：
We developed a facile bottom‐up strategy to synthesize Ni(II)‐incorporated covalent organic framework (LZU‐713@Ni) as heterogeneous all‐in‐one metallaphotoredox catalyst. LZU‐713@Ni showed excellent activity and recyclability in photoredox/nickel‐catalyzed C−O, C−S, and C−P cross‐coupling reactions. The superiority of bottom‐up strategy was exemplified by the increased activity of LZU‐713@Ni compared to both the dual catalyst system and LZU‐713/Ni prepared via post‐synthetic modification. Abstract The construction of an all‐in‐one catalyst, in which the photosensitizer and the transition metal site are close to each other, is important for improving the efficiency of metallaphotoredox catalysis. However, the development of convenient synthetic strategies for the precise construction of an all‐in‐one catalyst remains a challenging task due to the requirement of precise installation of the catalytic sites. Herein, we have successfully established a facile bottom‐up strategy for the direct synthesis of Ni(II)‐incorporated covalent organic framework (COF), named LZU‐713@Ni, as a versatile all‐in‐one metallaphotoredox catalyst. LZU‐713@Ni showed excellent activity and recyclability in the photoredox/nickel‐catalyzed C−O, C−S, and C−P cross‐coupling reactions. Notably, this catalyst displayed a better catalytic activity than its homogeneous analogues, physically mixed dual catalyst system, and, especially, LZU‐713/Ni which was prepared through post‐synthetic modification. The improved catalytic efficiency of LZU‐713@Ni should be attributed to the implementation of bottom‐up strategy, which incorporated the fixed, ordered, and abundant catalytic sites into its framework. This work sheds new light on the exploration of concise and effective strategies for the construction of multifunctional COF‐based photocatalysts.
作者：
Peng Chen;Mao-Mao Zhang;Wen-Jing Xiao;Liang-Qiu Lu
期刊：
中国科学：化学英文版,2024年EISCICSCD ISSN：1674-7291
作者机构：
Engineering Research Center of Photoenergy Utilization for Pollution Control and Carbon Reduction, Ministry of Education, College of Chemistry, Central China Normal University;Wuhan Institute of Photochemistry and Technology;State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of Sciences;School of Chemistry and Chemical Engineering, Henan Normal University
摘要：
＜正＞Chiral α-tertiary amines and related azacycles are commonly found in many natural products, pharmaceuticals and agrochemicals [1]. Copper-catalyzed asymmetric propargylic amination（APA） reactions have been established as a reliable method to access enantio-enriched propargylic amines,largely due to the seminal contribution of Nishibayashi et al.[2] and van Maarseveen et al. [3] in 2008.
摘要：
Radical-involved multicomponent difunctionalization of 1,3-dienes has recently emerged as a promising strategy for rapid synthesis of valuable allylic compounds in one-pot operation. However, the expansion of radical scope and enantiocontrol remain two major challenges. Herein, we describe an unprecedented photoinduced copper-catalyzed highly enantioselective three-component radical 1,2-azidooxygenation of 1,3-dienes with readily available azidobenziodazolone reagent and carboxylic acids. This mild protocol exhibits a broad substrate scope, high functional group tolerance, and exceptional control over chemo-, regio- and enantioselectivity, providing practical access to diverse valuable azidated chiral allylic esters. Mechanistic studies imply that the chiral copper complex is implicated as a bifunctional catalyst in both the photoredox catalyzed azidyl radical generation and enantioselective radical C-O cross-coupling. An unprecedented photoinduced copper-catalyzed asymmetric three-component radical 1,2-azidooxygenation of 1,3-dienes with readily available azidobenziodazolone reagent and carboxylic acids is reported. This process is notable for using chiral copper-based complex as a bifunctional catalyst for photoinduced azidyl radical generation and C-O cross-coupling, providing access to diverse valuable azidated chiral allylic esters. image
作者机构：
[Cheng, Ying; Yuan, Bao-Ru; Xiao, Wen-Jing; Xiao, WJ; He, Xiang-Kui] Cent China Normal Univ, Coll Chem, Engn Res Ctr Photoenergy Utilizat Pollut Control &, Minist Educ, Wuhan 430079, Peoples R China.;[Cheng, Ying; Xiao, Wen-Jing; Xiao, WJ] Wuhan Inst Photochem & Technol, Wuhan 430083, Peoples R China.
通讯机构：
[Cheng, Y; Xiao, WJ ] C;Cent China Normal Univ, Coll Chem, Engn Res Ctr Photoenergy Utilizat Pollut Control &, Minist Educ, Wuhan 430079, Peoples R China.;Wuhan Inst Photochem & Technol, Wuhan 430083, Peoples R China.
摘要：
A visible-light-induced synthesis protocol for silylmonofluoroalkanes is described. The silylation of alkenyl fluorides using (trimethylsilyl)silanes as organosilicon reagents proceeds well under mild conditions via a sequential photoinduced single-electron transfer and protonation process. The protocol shows a broad substrate scope, transition-metal-free conditions, and high functional group tolerance. A wide variety of silylmonofluoroalkanes were obtained in generally good yields (up to 82%).
摘要：
A mild strategy for the synthesis of boron‐handled pyrazoles through photocatalytic cascade radical cyclization of LBRs (Lewis base‐boryl radicals) with vinyldiazo reagents is described here. The reaction starts with the addition of LBRs at diazo site, followed by intramolecular radical cyclization to access a wide range of important boron‐handled pyrazoles in good to excellent yields. Control experiments, together with detailed mechanism studies well explain the observed reactivity. Abstract Vinyldiazo compounds are one of the most important synthons in the construction of a cyclic ring. Most photochemical transformations of vinyldiazo compounds are mainly focusing on utilization of their C═C bond site, while reactions taking place at terminal nitrogen atom are largely unexplored. Herein, a photocatalytic cascade radical cyclization of LBRs with vinyldiazo reagents through sequential B─N/C─N bond formation is described. The reaction starts with the addition of LBRs (Lewis base–boryl radicals) at diazo site, followed by intramolecular radical cyclization to access a wide range of important boron‐handled pyrazoles in good to excellent yields. Control experiments, together with detailed mechanism studies well explain the observed reactivity. Further studies demonstrate the utility of this approach for applications in pharmaceutical and agrochemical research.
通讯机构：
[Zhang, J ] T;[Chen, JR ] C;Taiyuan Univ Technol, Coll Biomed Engn, Taiyuan 030024, Peoples R China.;Cent China Normal Univ, Coll Chem, 152 Luoyu Rd, Wuhan 430079, Hubei, Peoples R China.
摘要：
The C(sp(3))-N bond is ubiquitous in natural products, pharmaceuticals, biologically active molecules and functional materials. Consequently, the development of practical and efficient methods for C(sp(3))-N bond formation has attracted more and more attention. Compared to the conventional ionic pathway-based thermal methods, photochemical processes that proceed through radical mechanisms by merging photoredox and transition-metal catalyses have emerged as powerful and alternative tools for C(sp(3))-N bond formation. In this review, recent advances in the burgeoning field of C(sp(3))-N bond formation via metallaphotoredox catalysis have been highlighted. The contents of this review are categorized according to the transition metals used (copper, nickel, cobalt, palladium, and iron) together with photocatalysis. Emphasis is placed on methodology achievements and mechanistic insight, aiming to inspire chemists to invent more efficient radical-involved C(sp(3))-N bond-forming reactions.
作者机构：
[Zhang, Zhi-Han; Lu, Liang-Qiu; Yu, Xu-Hui; Xiao, Wen-Jing; Shi, De-Qing] Cent China Normal Univ, Coll Chem, Key Lab Pesticide & Chem Biol, Minist Educ, 152 Luoyu Rd, Wuhan 430079, Hubei, Peoples R China.;[Xiao, Wen-Jing] Shanghai Inst Organ Chem, State Key Lab Organometall Chem, 345 Lingling Rd, Shanghai 200032, Peoples R China.
通讯机构：
[De-Qing Shi] K;Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei 430079, China
