作者机构：
[Gao, Yuan; Huan, Xiao-Die; Xiao, Wen-Jing; Chen, Jun; Chen, Jia-Rong; Wang, Peng-Zi] Cent China Normal Univ, CCNU uOttawa Joint Res Ctr, Key Lab Pesticides & Chem Biol, Minist Educ,Coll Chem, Wuhan, Hubei, Peoples R China.;[Xiao, Wen-Jing] Lanzhou Univ, State Key Lab Appl Organ Chem, Lanzhou, Peoples R China.
通讯机构：
[Xiao, Wen-Jing; Chen, Jia-Rong] C;CCNU-uOttawa Joint Research Centre, Key Laboratory of Pesticides & Chemical Biology Ministry of Education, College of Chemistry, Central China Normal University, Wuhan, Hubei, China.;State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou, China.
摘要：
The intermolecular three-component alkene vicinal dicarbofunctionalization (DCF) reaction allows installation of two different carbon fragments. Despite extensive investigation into its ionic chemistry, the enantioseletive radical-mediated versions of DCF reactions remain largely unexplored. Herein, we report an intermolecular, enantioselective three-component radical vicinal dicarbofunctionalization reaction of olefins enabled by merger of radical addition and cross-coupling using photoredox and copper dual catalysis. Key to the success of this protocol relies on chemoselective addition of acyl and cyanoalkyl radicals, generated in situ from the redox-active oxime esters by a photocatalytic N-centered iminyl radical-triggered C-C bond cleavage event, onto the alkenes to form new carbon radicals. Single electron metalation of such newly formed carbon radicals to TMSCN-derived L1Cu(II)(CN)(2) complex leads to asymmetric cross-coupling. This three-component process proceeds under mild conditions, and tolerates a diverse range of functionalities and synthetic handles, leading to valuable optically active beta -cyano ketones and alkyldinitriles, respectively, in a highly enantioselective manner (>60 examples, up to 97% ee). Vicinal dicarbofunctionalization (DCF) reactions of alkenes have been extensively explored in ionic chemistry but the enantioselective radical mediated version of DCF remains largely unexplored. Here, the authors demonstrate a radical vicinal DCF reaction of olefins by merging of radical addition and cross-coupling using photoredox and copper dual catalysis.
期刊：
Journal of the American Chemical Society,2021年143(11):4168-4173 ISSN：0002-7863
通讯作者：
Xiao, W.-J.
作者机构：
[Lu, Fu-Dong; Lu, Liang-Qiu; Bai, Jun-Chuan; Xiao, Wen-Jing; He, Gui-Feng] Cent China Normal Univ, Coll Chem, CCNU uOttawa Joint Res Ctr, Key Lab Pesticide & Chem Biol,Minist Educ, Wuhan 430079, 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.;[Xiao, Wen-Jing] Chinese Acad Sci, Shanghai Inst Organ Chem, State Key Lab Organometall Chem, Shanghai 200032, Peoples R China.
通讯机构：
[Xiao, W.-J.] C;CCNU-uOttawa Joint Research Centre, 152 Luoyu Road, China
摘要：
1,3-Dienes are readily available feedstocks that are widely used in the laboratory and industry. However, the potential of converting 1,3-dienes into value-added products, especially chiral products, has not yet been fully exploited. By synergetic photoredox/copper catalysis, we achieve the first visible-light-induced, enantioselective carbocyanation of 1,3-dienes by using carboxylic acid derivatives and trimethylsilyl cyanide. Under mild and neutral conditions, a diverse range of chiral allyl cyanides are produced in generally good efficiency and with high enantioselectivity from bench-stable and user-safe chemicals. Moreover, preliminary results also confirm that this success can be expanded to 1,3-enynes and the four-component carbonylative carbocyanation of 1,3-dienes and 1,3-enynes.
作者机构：
[Bao-Le Qu; Mao-Mao Zhang; Wen-Jing Xiao] 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, China;State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China;[Liang-Qiu Lu] 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, China<&wdkj&>State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China
通讯机构：
[Liang-Qiu Lu] 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, China<&wdkj&>State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China
摘要：
The 2,3-dihydrobenzofuran ring systems are a privileged class of oxygen heterocycles, and their synthesis continues to attract considerable effort. Herein, a visible-light-driven photoredox-catalyzed radical multicomponent cyclization of 2-vinyl phenols, N-alkoxypyridinium salts, and sulfur ylides is described. The key to the reaction success involves the use of both N-alkoxypyridinium salts and sulfur ylides as radical precursors. This redox-neutral protocol features good functional group tolerance, easily available starting materials, simple operation, and mild reaction conditions, enabling the modular synthesis of various 2,3-disubstituted dihydrobenzofurans. Mechanistic studies have also elucidated some of the aspects associated with the key radical intermediates.
摘要：
A formal [4+3]-cycloaddition reaction of ortho-hydroxyphenyl-substituted para-quinone methides (p-QMs) with in-situ generated azaoxyallyl cations is reported. The reaction occurs under very mild reaction conditions (transition-metal free, room temperature, cheap inorganic base) and provides a very efficient route to a series of biologically important 1,4-benzoxazepine derivatives in good to excellent yields.
作者机构：
[贾玥; 肖文精; 姜烜] CCNU-uOttawa Joint Research Centre, Key Laboratory of Pesticides & 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, Chinese Academy of Sciences, Lanzhou, 730000, China;[陆良秋] CCNU-uOttawa Joint Research Centre, Key Laboratory of Pesticides & 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, Chinese Academy of Sciences, Lanzhou, 730000, China
通讯机构：
[Lu, L.-Q.] C;CCNU-uOttawa Joint Research Centre, Key Laboratory of Pesticides & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan, China
摘要：
Carbon monoxide,as a C1 synthon,plays a fundamentally important role in modern chemical synthesis.Despite great achievements,the development of sustainable and effective CO conversion methods is still in high demand.Transitionmetal-catalyzed carbonylation of halides has been established as a powerful platform for assembling valuable carbonyl compounds,including(thio)esters,amides,aldehydes and ketones.Nevertheless,high barrier owing to the strong coordination of CO with transition metals would disfavor the oxidative addition of metal catalysts to halides,which results in the requirements of high temperature and highly active substrate.In the past decades,Alexanian groups and Ryu groups,respectively used electron-rich catalysts and ultraviolet light to facilitate oxidative addition,realizing carbonylation of alkyl iodines with strong nucleophilic reagents.Research has also shown that the use of sterically hindered ligands can accelerate the reductive elimination to generate acyl halides.However,these ligands disfavor the occurrence of oxidative addition and limit the range of reaction substrates.To date,all these results indicate that there is no magic power that can simultaneously promote oxidative addition and reductive elimination.
期刊：
Angewandte Chemie - International Edition,2020年 ISSN：1433-7851
作者机构：
[Lu, Liang-Qiu] Central China Normal University, CCNU-uOttawa Joint Research Centre, Key Laboratory of Pesticides and Chemical Biology, 152 Luoyu Road, 430079, Wuhan, Hubei, CHINA;[Qu, Bao-Le; Xiao, Wen-Jing; Li, Miao-Miao; Xiao, Yu-Qing] Central China Normal University, College of Chemistry, CHINA;[Xiong, Qin] Chongqing University, School of Chemistry and Chemical Engineering, CHINA;[Lan, Yu] Zhengzhou University, College of Chemistry, CHINA
摘要：
Vinylcyclopropanes (VCPs) are commonly used in transition metal-catalyzed cycloadditions, and the exploitation of their recently realized reactivities to construct new cyclic architectures is of great significance in modern synthetic chemistry. Herein, a palladium-catalyzed, visible light-driven, asymmetric [5+2] cycloaddition of VCPs with α-diazoketones was first accomplished by switching the reactivity of the Pd-containing dipolar intermediates from all-carbon 1,3-dipoles to oxo-1,5-dipoles. Enantioenriched 7-membered lactones were produced with good reaction efficiency and selectivity (23 examples, 52-92% yields with up to 99:1 er and 12.5:1 dr). In addition, computational investigations were performed to rationalize the observed high chemo- and periselectivities.
作者机构：
[Mukund M. D. Pramanik; Hao Qian; Wen-Jing Xiao; Jia-Rong Chen] CCNU-uOttawa Joint Research Center, Key Laboratory of Pesticides & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei 430079, China
通讯机构：
[Wen-Jing Xiao; Jia-Rong Chen] C;CCNU-uOttawa Joint Research Center, Key Laboratory of Pesticides & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei 430079, China
摘要：
New photoinduced strategies towards radical reactions of strained molecules such as [1.1.1]propellane and bicyclo[1.1.0]butanes by photoredox or metallaphotoredox catalysis have recently been disclosed. Such strategies enable the controllable construction of 1,3-difunctionalized bicyclo[1.1.1]pentanes, cyclobutanes, and drug-like analogues, and offer new opportunities for reaction design of [1.1.1]propellane and other strained molecules.
期刊：
Green Synthesis and Catalysis,2020年1(1):42-51 ISSN：2666-5549
作者机构：
CCNU-uOttawa Joint Research Centre, Key Laboratory of Pesticides & Chemical Biology Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, China;State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Shanghai 200032, China
摘要：
Visible-light photoredox catalysis is a powerful and attractive strategy for organic molecule activation and new reaction design owing to its environmental-friendly characteristics and unique catalytic mechanisms, and has found wide applications in organic synthesis. This catalytic strategy enables controllable generation of diverse nitrogen-centered radicals (NCRs) under mild conditions, providing access to construction of diverse nitrogen-containing compounds. In this review, we critically illustrate the recent advances in the field of visible-light photoredox-catalyzed cyclization of nitrogen-centered radicals, based on the different radical precursors and activation modes. Wherever possible, particular emphasis is also put on working models and synthetic applications.
作者机构：
[Yuan, Fan; Xiao, Wen-Jing; Chen, Jia-Rong; Yan, Dong-Mei; Pramanik, Mukund M. D.] Cent China Normal Univ, CCNU uOttawa Joint Res Ctr, Hubei Int Sci & Technol Cooperat Base Pesticide &, Key Lab Pesticides & Chem Biol,Minist Educ,Coll C, Wuhan 430079, Hubei, Peoples R China.;[Xiao, Wen-Jing] Shanghai Inst Organ Chem, State Key Lab Organometall Chem, Shanghai 200032, Peoples R China.
通讯机构：
[Chen, Jia-Rong] C;Cent China Normal Univ, CCNU uOttawa Joint Res Ctr, Hubei Int Sci & Technol Cooperat Base Pesticide &, Key Lab Pesticides & Chem Biol,Minist Educ,Coll C, Wuhan 430079, Hubei, Peoples R China.
摘要：
A visible-light-driven photoredox-catalyzed multicomponent reaction of 2-vinylanilines, sulfonyl chlorides, and sulfur ylides is described. This protocol features redox-neutral mild conditions, a broad substrate scope, and good functional group tolerance, providing access to various sulfonated 2,3-disubstituted indolines. The product can be transformed to a diverse range of functionalized indoles by a selective aromatization/nucleophilic substitution process. Mechanistic investigations suggest that both sulfonyl chlorides and sulfur ylides serve as radical sources, and the reaction proceeds through a sequential radical addition/addition/thermal SN2-substitution process.
作者机构：
[Zhao, Quan-Qing; Xu, Shuang-Hua; Xiao, Wen-Jing; Chen, Jia-Rong; Zhou, Xue-Song; Wu, Ya-Li] Cent China Normal Univ, Coll Chem, CCNU uOttawa Joint Res Ctr, Minist Educ,Key Lab Pesticides & Chem Biol, Wuhan 430079, Hubei, Peoples R China.;[Xiao, Wen-Jing] Lanzhou Univ, State Key Lab Appl Organ Chem, Lanzhou 730000, Peoples R China.
通讯机构：
[Chen, Jia-Rong] C;Cent China Normal Univ, Coll Chem, CCNU uOttawa Joint Res Ctr, Minist Educ,Key Lab Pesticides & Chem Biol, Wuhan 430079, Hubei, Peoples R China.
摘要：
A visible light photoredox-promoted and nitrogen radical catalyzed [3 + 2] cyclization of vinylcyclopropanes and N-tosyl vinylaziridines with alkenes is developed. Key to the success of this process is the use of the readily tunable hydrazone as a nitrogen radical catalyst. Preliminary mechanism studies suggest that the photogenerated nitrogen radical undergoes reversible radical addition to the vinylcyclopropanes and N-tosyl vinylaziridines to enable their ring-opening C-C and C-N bond cleavage and ensuing cyclization with alkenes.
摘要：
Higher-order cycloadditions, particularly [8+2] cycloadditions, are a straightforward and efficient strategy for constructing significant medium-sized architectures. Typically, configuration-restrained conjugated systems are utilized as 8π-components for higher-order concerted cycloadditions. However, for this reason, 10-membered monocyclic skeletons have never been constructed via catalytic asymmetric [8+2] cycloaddition with high peri- and stereoselectivity. Here, we accomplished an enantioselective [8+2] dipolar cycloaddition via the merger of visible-light activation and asymmetric palladium catalysis. This protocol provides a new route to 10-membered monocyclic architectures bearing chiral quaternary stereocenters with high chemo-, peri-, and enantioselectivity. The success of this strategy relied on the facile in situ generation of Pd-containing 1,8-dipoles and their enantioselective trapping by ketene dipolarophiles, which were formed in situ via a photo-Wolff rearrangement.
摘要：
. Summary of main observation and conclusion: An enantioselective deoxygenative cyanation of benzyl alcohols was accomplished for the first time through the synergistic photoredox and copper catalysis. This reaction features the use of organic photosensitizer and low-cost 3d metal catalyst, simple and safe operations, and extremely mild conditions. A variety of chiral benzyl nitriles were produced in generally good yields and high level of enantiocontrols from readily available feedstocks (22 examples, up to 93% yield and 92% ee).
