期刊：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2023年145(22):12233-12243 ISSN：0002-7863
通讯作者：
Xiao, Wen-Jing;Chen, JR;Jiang, M;Xiao, WJ
作者机构：
[Qu, Wen-Yuan; Xiao, Wen-Jing; Chen, Jia-Rong; Zhou, Xue-Song; Liu, Xiao-Peng; Xiao, WJ; 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, Zhejiang, Peoples R China.;[Xiao, Wen-Jing; Chen, Jia-Rong; Xiao, WJ; Chen, JR] Wuhan Inst Photochem & Technol, Wuhan 430083, Hubei, Peoples R China.;[Xiao, Wen-Jing; Xiao, WJ] Shanghai Inst Organ Chem, State Key Lab Organometall Chem, Shanghai 200032, Peoples R China.;[Chen, Jia-Rong; Chen, JR] Henan Normal Univ, Sch Chem & Chem Engn, Xinxiang 453007, Peoples R China.
通讯机构：
[Jiang, M ] H;[Xiao, WJ ] S;[Xiao, WJ; Chen, JR ] C;Cent China Normal Univ, Coll Chem, Wuhan 430079, Hubei, Peoples R China.;Hangzhou Normal Univ, Coll Mat Chem & Chem Engn, Hangzhou 310036, Zhejiang, Peoples R China.
通讯作者：
Prof. Jia-Rong Chen<&wdkj&>Prof. Jia-Rong Chen Prof. Jia-Rong Chen Prof. Jia-Rong Chen
作者机构：
[Bin Lu; Prof. Zhihan Zhang; Dong Liang; Zi-Wei He; Feng-Shuo Bao; Bin Lu Bin Lu Bin Lu; Prof. Zhihan Zhang Prof. Zhihan Zhang Prof. Zhihan Zhang; Dong Liang Dong Liang Dong Liang; Zi-Wei He Zi-Wei He Zi-Wei He; Feng-Shuo Bao Feng-Shuo Bao Feng-Shuo Bao] Engineering Research Center of Photoenergy Utilization for Pollution Control and Carbon Reduction, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei, 430079 China;College of Materials, Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou, 310036 China;Wuhan Institute of Photochemistry and Technology, 7 North Bingang Road, Wuhan, Hubei, 430083 China;School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, 453007 China;[Prof. Min Jiang; Prof. Min Jiang Prof. Min Jiang Prof. Min Jiang] Engineering Research Center of Photoenergy Utilization for Pollution Control and Carbon Reduction, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei, 430079 China<&wdkj&>College of Materials, Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou, 310036 China
通讯机构：
[Prof. Jia-Rong Chen; Prof. Jia-Rong Chen Prof. Jia-Rong Chen Prof. Jia-Rong Chen] E;Engineering Research Center of Photoenergy Utilization for Pollution Control and Carbon Reduction, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei, 430079 China<&wdkj&>Wuhan Institute of Photochemistry and Technology, 7 North Bingang Road, Wuhan, Hubei, 430083 China<&wdkj&>School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, 453007 China
摘要：
<jats:title>Abstract</jats:title><jats:p>Radical single carbonylation reactions with CO constitute a direct and robust strategy toward various carbonyl compounds from readily available chemicals, and have been extensively studied over the past decades. However, realizing highly selective catalytic systems for controlled radical double carbonylation reactions has remained a substantial challenge, particularly for the more advanced multicomponent variants, despite their great potential value. Herein, we report a visible‐light‐driven radical relay five‐component radical double aminocarbonylation reaction of unactivated alkenes using CO under metal‐free conditions. This protocol provides direct access to valuable γ‐trifluoromethyl α‐ketoamides with good yields and high chemoselectivity. Crucial was the identification of distinct dual roles of amine coupling partners, sequentially acting as electron donors for the formation of photoactive electron donor‐acceptor (EDA) complexes with radical precursors and then as a CO acceptor via nitrogen radical cations to form carbamoyl radicals. Cross‐coupling of carbamoyl radicals with the acyl radicals that are formed in an alkene‐based relay process affords double aminocarbonylation products.</jats:p>
作者机构：
[Lu, Liang-Qiu; Lu, LQ; He, Lin; Qu, Bao-Le; Xiao, Wen-Jing; Shi, Jun-Wei; Shi, Bin] Cent China Normal Univ, Coll Chem, CCNU uOttawa Joint Res Ctr, Key Lab Pesticide & Chem Biol, Wuhan 430079, Hubei, Peoples R China.;[Lu, Liang-Qiu] Henan Normal Univ, Sch Chem & Chem Engn, Xinxiang 453007, Henan, Peoples R China.;[Lu, Liang-Qiu] Chinese Acad Sci, Lanzhou Inst Chem Phys LICP, State Key Lab Oxo Synth & Select Oxidat, Lanzhou 730000, Gansu, Peoples R China.
通讯机构：
[Lu, LQ ] C;Cent China Normal Univ, Coll Chem, CCNU uOttawa Joint Res Ctr, Key Lab Pesticide & Chem Biol, Wuhan 430079, Hubei, Peoples R China.
摘要：
Indoline skeletons are widely found in many natural isolates and pharmaceuticals, making indoline synthesis an ongoing research hotspot in synthetic chemistry. However, the catalytic asymmetric de novo construction of indolines bearing chiral quaternary stereocenters remains challenging. Herein, we present a solution to this unmet challenge through copper-catalyzed asymmetric [4 + 1] cycloadditions of ethynylbenzoxazinones with sulfur ylides, which are formed in situ by photoinduced carbene transfer. As a result, a wide range of chiral indolines bearing C2-quaternary stereocenters are obtained with good enantio- and diastereoselectivities (up to 19 : 1 dr and 96 : 4 er).
作者机构：
[Xiao, Wen-Jing; Chen, Jia-Rong; Wang, Peng-Zi] Cent China Normal Univ, Coll Chem, Key Lab Pesticides & Chem Biol, Minist Educ, Wuhan, Peoples R China.;[Chen, Jia-Rong] Henan Normal Univ, Sch Chem & Chem Engn, Xinxiang, Henan, Peoples R China.
通讯机构：
[Wen-Jing Xiao; Jia-Rong Chen] K;Key Laboratory of Pesticides & Chemical Biology Ministry of Education, College of Chemistry, Central China Normal University, Wuhan, China<&wdkj&>School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, China<&wdkj&>Key Laboratory of Pesticides & Chemical Biology Ministry of Education, College of Chemistry, Central China Normal University, Wuhan, China
摘要：
Creating, conserving and modifying the stereochemistry of organic compounds has been the subject of significant research efforts in synthetic chemistry. Most synthetic routes are designed according to the stereoselectivity-determining step. Stereochemical editing is an alternative strategy, wherein the chiral-defining or geometry-defining steps are independent of the construction of the major scaffold or complexity. It enables late-stage alterations of stereochemistry and can generate isomers from a single compound. However, in many instances, stereochemical editing processes are contra-thermodynamic, meaning the transformation is unfavourable. To overcome this barrier, photocatalysis uses photogenerated radical species and introduces thermochemical biases. A range of synthetically valuable contra-thermodynamic stereochemical editing processes have been invented, including deracemization of chiral molecules, positional alkene isomerization and dynamic epimerization of sugars and diols. In this Review, we highlight the fundamental mechanisms of visible-light photocatalysis and the general reactivity modes of the photogenerated radical intermediates towards contra-thermodynamic stereochemical editing processes. Stereochemical editing is a strategy to access three-dimensional skeletons, where the stereochemistry-defining steps are decoupled from the major connectivity-forming reactions. This Review highlights recent advances in the area of light-driven contra-thermodynamic stereochemical editing.
作者机构：
[Xiao, Wen-Jing; Chen, Jia-Rong; Wang, Peng-Zi] Cent China Normal Univ, Coll Chem, 152 Luoyu Rd, Wuhan 430079, Hubei, Peoples R China.;[Xiao, Wen-Jing; Chen, Jia-Rong] Wuhan Inst Photochem & Technol, 7 North Bingang Rd, Wuhan 430082, Hubei, Peoples R China.
通讯机构：
[Prof. Dr. Wen-Jing Xiao; Prof. Dr. Jia-Rong Chen] C;College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei, 430079 China<&wdkj&>Wuhan Institute of Photochemistry and Technology, 7 North Bingang Road, Wuhan, Hubei, 430082 China
摘要：
<jats:title>Abstract</jats:title><jats:p>Catalytic and switchable C−H functionalization of <jats:italic>N</jats:italic>‐heteroarenes under easily tunable conditions is a robust but challenging tool for the construction of biologically relevant compounds. Recently, a general electrochemical strategy has been developed for the direct C−H carboxylation of <jats:italic>N</jats:italic>‐heteroarenes with CO<jats:sub>2</jats:sub>, and by simply choosing different types of cell setups, carboxylated products are furnished with excellent and tunable site selectivity. This study also paves the way for regulating the reactivity modes in electrochemical synthesis.</jats:p>
作者机构：
[Li, Guo-Qing; Meng, Fan-Rong; Xiao, Wen-Jing; Chen, Jia-Rong; Chen, JR] Cent China Normal Univ, Coll Chem, 152 Luoyu Rd, Wuhan 430079, Hubei, Peoples R China.;[Chen, Jia-Rong; Chen, JR] Gannan Normal Univ, Key Lab Organo Pharmaceut Chem Jiangxi Prov, Ganzhou 341000, Peoples R China.;[Chen, Jia-Rong; Chen, JR] Henan Normal Univ, Sch Chem & Chem Engn, Xinxiang 453007, Henan, Peoples R China.
通讯机构：
[Chen, JR ] C;Cent China Normal Univ, Coll Chem, 152 Luoyu Rd, Wuhan 430079, Hubei, Peoples R China.;Gannan Normal Univ, Key Lab Organo Pharmaceut Chem Jiangxi Prov, Ganzhou 341000, Peoples R China.;Henan Normal Univ, Sch Chem & Chem Engn, Xinxiang 453007, Henan, Peoples R China.
摘要：
Catalytic radical difunctionalization of 1,3-enynes has recently been established as a potentially robust platform for construction of valuable allenes and propargylic compounds. Despite the considerable advances made in the realm of radical 1,4-difunctionalizations, there has been little progress in the radical 1,2-difunctionalizations, particularly regarding enantioselective variants. Herein, we report the first regio- and enantioselective radical three-component coupling of 1,3-enynes, oxime esters, and carboxylic acids through photoinduced copper catalysis. This redox-neutral protocol proceeds under mild conditions and demonstrates good functional group tolerance and 1,2-regioselectivity, providing access to a library of valuable cyanoalkylated propargylic esters with generally excellent enantioselectivity (>60 examples; up to 99% ee).
期刊：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2023年145(32):17527-17550 ISSN：0002-7863
通讯作者：
Chen, Jia-Rong;Xiao, WJ
作者机构：
[Xiao, Wen-Jing; Chen, Jia-Rong; Wang, Peng-Zi] Cent China Normal Univ, Coll Chem, Wuhan 430079, Hubei, Peoples R China.;[Xiao, Wen-Jing; Chen, Jia-Rong] Wuhan Inst Photochem & Technol, Wuhan 430083, Hubei, Peoples R China.;[Xiao, Wen-Jing] Lanzhou Univ, State Key Lab Appl Organ Chem, Lanzhou 730000, Peoples R China.;[Chen, JR; Xiao, WJ] Cent China Normal Univ, Coll Chem, Wuhan 430079, Hubei, Peoples R China.;[Chen, JR; Xiao, WJ] Wuhan Inst Photochem & Technol, Wuhan 430083, Hubei, Peoples R China.
通讯机构：
[Chen, JR; Xiao, WJ ] ;Cent China Normal Univ, Coll Chem, Wuhan 430079, Hubei, Peoples R China.;Wuhan Inst Photochem & Technol, Wuhan 430083, Hubei, Peoples R China.;Lanzhou Univ, State Key Lab Appl Organ Chem, Lanzhou 730000, Peoples R China.
摘要：
The C-O bond is ubiquitous in biologically active molecules, pharmaceutical agents, and functional materials, thereby making it an important functional group. Consequently, the development of C-O bond-forming reactions using catalytic strategies has become an increasingly important research topic in organic synthesis because more conventional methods involving strong base and acid have many limitations. In contrast to the ionic-pathway-based methods, copper-promoted radical-mediated C-O bond formation is experiencing a surge in research interest owing to a renaissance in free-radical chemistry and photoredox catalysis. This Perspective highlights and appraises state-of-the-art techniques in this burgeoning research field. The contents are organized according to the different reaction types and working models.
摘要：
The exploration of value‐added conversions of naturally abundant amino acids has received considerable attention from the synthetic community. Compared with the well‐established asymmetric decarboxylative transformation, the asymmetric deaminative transformation of amino acids still remains a formidable challenge, mainly due to the lack of effective strategies for the C‐N bond activation and the potential incompatibility with chiral catalysts. Here, we disclose a photoinduced Cu‐catalyzed asymmetric deaminative coupling reaction of amino acids with arylboronic acids. This new protocol provides a series of significant chiral phenylacetamides in generally good yields and excellent stereoselectivity under mild and green conditions (42‐85% yields, up to 97% ee). Experimental investigations and theoretical calculations were performed to reveal the crucial role of additional phenols in improving catalytic efficiency and enantiocontrol.
期刊：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2023年145(14):7983-7991 ISSN：0002-7863
通讯作者：
Ke Gao<&wdkj&>Wen-Jing Xiao
作者机构：
[Lu, Liang-Qiu; Gao, Ke; Cheng, Ying; Jiang, Xuan; Xiao, Wen-Jing; Wang, Wen-Cheng; Xiong, Wei] Cent China Normal Univ, Coll Chem, CCNU uOttawa Joint Res Ctr, Key Lab Pesticide & Chem Biol,Minist Educ, Wuhan 430079, Peoples R China.;[Xiao, Wen-Jing] Shanghai Inst Organ Chem, State Key Lab Organometall Chem, Shanghai 200032, Peoples R China.
通讯机构：
[Ke Gao; Wen-Jing Xiao] C;CCNU-uOttawa Joint Research Centre, Key Laboratory of Pesticide and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan 430079, P. R. China<&wdkj&>CCNU-uOttawa Joint Research Centre, Key Laboratory of Pesticide and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan 430079, P. R. China<&wdkj&>State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, 345 Lingling Road, Shanghai 200032, P. R. China
摘要：
Conjugate addition is among the most important synthetic protocols for constructing carbon skeletons and is widely used to synthesize natural products and drugs. However, asymmetric catalysis studies have mainly focused on constructing stereogenic centers arising from conjugate alkenes. Here, we report the first photoinduced cobalt-catalyzed dynamic kinetic reductive conjugate addition reaction that enables the formation of heterobiaryls with axial chirality (45 examples, up to 91% yield and 97% ee). This method features mild reaction conditions, good functional-group tolerance, and excellent enantiomeric control. Significantly, large amounts of metal waste and precious metal catalysts can be avoided under these conditions. Migration of the chiral arylcobalt species into the alkene might be the rate-determining step based on kinetic studies.
期刊：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2023年145(12):6944-6952 ISSN：0002-7863
通讯作者：
Ying Cheng<&wdkj&>Wen-Jing Xiao
作者机构：
[Zhao, Wei; Lu, Liang-Qiu; Cheng, Ying; Jiang, Xuan; Xiao, Wen-Jing; He, Xiang-Kui; Jiang, Hao] Cent China Normal Univ, Coll Chem, CCNU uOttawa Joint Res Ctr, Key Lab Pesticide & Chem Biol,Minist Educ, R China, Wuhan 430079, Peoples R China.;[Lu, Liang-Qiu; Cheng, Ying; Xiao, Wen-Jing] Wuhan Inst Photochem & Technol, Wuhan 430083, Peoples R China.
通讯机构：
[Ying Cheng; Wen-Jing Xiao] C;CCNU-uOttawa Joint Research Centre, Key Laboratory of Pesticide and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan 430079, P. R. China<&wdkj&>Wuhan Institute of Photochemistry and Technology, 7 Bingang North Road, Wuhan 430083, P. R. China
摘要：
Enantioselective metallaphotoredox catalysis, which combines photoredox catalysis and asymmetric transition-metal catalysis, has become an effective approach to achieve stereoconvergence under mild conditions. Although many impressive synthetic approaches have been developed to access central chirality, the construction of axial chirality by metallaphotoredox catalysis still remains underexplored. Herein, we report two visible light-induced cobalt-catalyzed asymmetric reductive couplings of biaryl dialdehydes to synthesize axially chiral aldehydes (60 examples, up to 98% yield, >19:1 dr, and >99% ee). This protocol shows good functional group tolerance, broad substrate scope, and excellent diastereo- and enantioselectivity.
作者：
Yi Wei;Fen-Ya Xiong;Liang-Qiu Lu*;Wen-Jing Xiao
期刊：
Chem,2023年9(3):559-561 ISSN：2451-9294
通讯作者：
Liang-Qiu Lu
作者机构：
[Yi Wei; Fen-Ya Xiong; Wen-Jing Xiao] CCNU-uOttawa Joint Research Center, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei 430079, China;School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, Henan 453007, China;[Liang-Qiu Lu] CCNU-uOttawa Joint Research Center, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei 430079, China<&wdkj&>School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, Henan 453007, China
通讯机构：
[Liang-Qiu Lu] C;CCNU-uOttawa Joint Research Center, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei 430079, China<&wdkj&>School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, Henan 453007, China
摘要：
The direct allylic C–H amination of alkenes, especially internal ones, with aliphatic amines remains a major challenge in chemical synthesis. Recently in Science, Gevorgyan et al. reported a robust strategy for this process with photoinduced palladium catalysis, which accommodates different olefin substitution patterns and offers excellent selectivities.
作者机构：
[Xiong W.; Chen P.; Zhang M.-M.; Hui X.-S.] CCNU-uOttawa Joint Research Centre, Key Laboratory of Pesticide and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan, 430079, China;State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of Sciences, Lanzhou, 730000, China;State Key Laboratory of Applied Organic Chemistry, Department of Chemistry, Lanzhou University, Lanzhou, 730000, China;[Lu L.-Q.] CCNU-uOttawa Joint Research Centre, Key Laboratory of Pesticide and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan, 430079, China, State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of Sciences, Lanzhou, 730000, China;[Xiao W.-J.] CCNU-uOttawa Joint Research Centre, Key Laboratory of Pesticide and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan, 430079, China, State Key Laboratory of Applied Organic Chemistry, Department of Chemistry, Lanzhou University, Lanzhou, 730000, China
通讯机构：
[Lu, L.-Q.] C;CCNU-uOttawa Joint Research Centre, China
作者机构：
[Cheng, Ying; Rao, Li; Xiao, Wen-Jing; Chen, Jia-Rong; Wu, Ya-Li] Cent China Normal Univ, Coll Chem, Minist Educ, CCNU uOttawa Joint Res Ctr,Key Lab Pesticides & Ch, Wuhan 430079, Peoples R China.;[Jiang, Min] Hangzhou Normal Univ, Coll Mat Chem & Chem Engn, Hangzhou 310036, Peoples R China.;[Chen, Jia-Rong] Henan Normal Univ, Sch Chem & Chem Engn, Xinxiang 453007, Peoples R China.
通讯机构：
[Jia-Rong Chen] C;CCNU-uOttawa Joint Research Centre, Key Laboratory of Pesticides & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, P. R. China<&wdkj&>School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang 453007, P. R. China
摘要：
A three-component 1,2-aminooxygenation reaction of 1,3-dienes by dual photoredox and copper catalysis is described. This protocol uses N-aminopyridinium salts as N-centered radical precursors and nucleophilic alcohols as oxygen sources, providing modular and practical access to 1,2-aminoalkoxylation products with good yields and regioselectivity. Preliminary mechanistic studies support the radical property of the reaction and the involvement of N-centered radical intermediates.
作者机构：
[Lu, Liang-Qiu; Xiong, Feng-Ya; Wang, Bao-Cheng; Qu, Bao-Le; Xiao, Wen-Jing; Wei, Yi] Cent China Normal Univ, Coll Chem, Key Lab Pesticide & Chem Biol, Minist Educ, Wuhan 430079, Peoples R China.;[Xiao, Wen-Jing] Chinese Acad Sci, Univ Chinese Acad Sci, Shanghai Inst Organ Chem, State Key Lab Organometall Chem, Shanghai 200032, Peoples R China.;[Lu, Liang-Qiu] Henan Normal Univ, Sch Chem & Chem Engn, Xinxiang 453007, Henan, Peoples R China.;[Lu, Liang-Qiu] Chinese Acad Sci, Lanzhou Inst Chem Phys LICP, State Key Lab Oxo Synth & Select Oxidat, Lanzhou 730000, Peoples R China.
通讯机构：
[Liang-Qiu Lu] K;Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan, China<&wdkj&>School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, China<&wdkj&>State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of Sciences, Lanzhou, China
摘要：
Concise synthesis of eight-membered lactones, a kind of medium-sized heterocycles widespread in many bioactive natural products, is highly significant. However, it still remains a challenge due to unfavorable entropic factor and transannular interaction. Herein, we disclose an enantioselective synthesis of eight-membered lactones through a Pd-catalyzed asymmetric (6+2) dipolar annulation of vinyl oxetanes and alpha-diazo ketones (20 examples, up to 93% yield and 95:5 er). This reaction features simple operation, mild conditions and good enantiocontrol, especially the challenging chiral all-carbon quaternary stereocenter. A newly developed chiral hybrid P,S ligand and the in-situ photo-generation of ketene dipolarophiles are crucial to this success.
