Article
Chemistry, Physical
Huan Zhou, Zhong-Liang Li, Qiang-Shuai Gu, Xin-Yuan Liu
Summary: Transition-metal-catalyzed asymmetric C-(sp(3))-C cross-coupling is an efficient method for the rapid synthesis of enantioenriched molecules. Chiral copper catalysts have been designed to promote a variety of asymmetric radical C(sp(3))-C cross-coupling reactions with high efficiency and enantioselectivity. The key to success lies in the design of chiral ligands to initiate the reaction and achieve enantiocontrol over the highly reactive prochiral alkyl radical species.
Review
Chemistry, Applied
Yuxue Cao, Guodu Liu
Summary: Chiral phosphoric acid has been a crucial catalyst in chemical synthesis for over five decades. However, a revolutionary approach using photocatalytic excitation of molecules to generate free radicals has emerged in recent years, surpassing the limitations of traditional organic synthesis methods. A significant area of research focuses on chiral phosphoric acid synergistic photocatalysis for enantioselective chemical synthesis, utilizing a bifunctional hydrogen-bonding catalyst.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Shuai Zhang, Nan Jiang, Jun-Zhao Xiao, Guo-Qiang Lin, Liang Yin
Summary: Herein, a copper(I)-catalyzed asymmetric hydrophosphination method for 3,3-disubstituted cyclopropenes is reported. The method provides phosphine derivatives with high diastereo- and enantioselectivities. It has a broad substrate scope and the high stereoselectivity is attributed to the stability and asymmetric induction of the Cu(I)-(R,R)-QUINOXP* complex. The method is also used for the synthesis of new chiral phosphine-olefin compounds, which serve as ligands in Rh-catalyzed asymmetric conjugate addition reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Shuai Zhang, Nan Jiang, Jun-Zhao Xiao, Guo-Qiang Lin, Liang Yin
Summary: A copper(I)-catalyzed asymmetric hydrophosphination of 3,3-disubstituted cyclopropenes is reported, providing a range of highly selective phosphine derivatives. The method shows broad substrate scope and the high stereoselectivity is attributed to the stability of the Cu(I)-(R,R)-QUINOXP* complex and its asymmetric induction. Finally, the method is used for the synthesis of new chiral phosphine-olefin compounds, one of which serves as a wonderful ligand in Rh-catalyzed asymmetric conjugate addition.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Yan-Bo Li, Hu Tian, Shuai Zhang, Jun-Zhao Xiao, Liang Yin
Summary: In this study, a copper(I)-catalyzed reaction of diarylphosphines and O-benzoyl hydroxylamines was developed, leading to the synthesis of aminophosphinites and P-chiral aminophosphinites. The reaction mechanism was proposed and further transformation to P-chiral phosphines was achieved.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Multidisciplinary
Hirohisa Ohmiya, Masaya Sawamura
Summary: This study focuses on the application of alkylboranes in addition reactions to unsaturated compounds, catalyzed by copper. Alkylboranes can be easily obtained from standard alkene hydroboration reactions, and the substrates can encompass a wide range of functional groups. The reactions involve the formation of alkylcopper(I) species through catalytic B/Cu transmetallation of alkylboranes and subsequent addition to unsaturated carbon-carbon bonds or carbon dioxide.
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN
(2021)
Article
Chemistry, Multidisciplinary
Si-Qing Wang, Zong-Ci Liu, Wen-Jun Yue, Liang Yin
Summary: This study reveals a vinylogous aldol-type reaction for the synthesis of chiral gamma-hydroxyl-alpha,beta-unsaturated azaarenes with high selectivity and yields. The use of different ligands can control the formation of the carbon-carbon double bond in the products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Multidisciplinary
Xueling Mo, Rui Guo, Guozhu Zhang
Summary: Alkynes are important functional groups in organic chemistry and there have been significant efforts in synthesizing chiral alkynes. The asymmetric C(sp(3))-C(sp) cross-coupling offers a complementary strategy through radical-initiated process. However, controlling the stereochemistry of highly reactive and unstable radical intermediates has been a long-standing challenge. In order to address this problem, various chiral ligands have been developed to initiate the reaction and achieve enantiocontrol of alkyl radicals. This review summarizes recent developments in copper-catalyzed enantioselective alkynylation of prochiral alkyl radicals and provides insights into the mechanism.
CHINESE JOURNAL OF CHEMISTRY
(2023)
Review
Chemistry, Multidisciplinary
Yan-Nan Zheng, Hongxing Zheng, Ting Li, Wen-Ting Wei
Summary: C-N bonds are widely present in organic materials, natural products, pharmaceutical compounds, and agricultural chemicals. The development of greener and more convenient ways to form C-N bonds, particularly in late-stage synthesis, has become a hot research topic in synthetic chemistry. Copper-catalyzed radical reactions involving N-centered radicals are considered as a sustainable and promising approach for building C-N bonds.
Article
Chemistry, Multidisciplinary
Zhi-Zhou Pan, Jia-Heng Li, Hu Tian, Liang Yin
Summary: A copper(I)-catalyzed asymmetric allylation of ketones with 2-aza-1,4-dienes has been demonstrated, providing a series of functionalized homoallyl tertiary alcohols with high to excellent enantioselectivity. The deprotonation of N-allyl-1,1-diphenylmethanimines is the rate-determining step in the reaction, generating nucleophilic allyl copper(I) species. The utility of this method has been demonstrated by the asymmetric synthesis of (R)-boivinianin A and (R)-gossonorol.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Dunqi Wu, Lianqian Wu, Pinhong Chen, Guosheng Liu
Summary: Alkynes play important roles in natural products and organic synthesis, but the enantioselective construction of alkyne substituted all carbon quaternary stereocenters has been a challenging task in asymmetric radical reactions. In this study, we discovered that introducing an amidyl group next to the tertiary carbon radical enables the asymmetric radical coupling with alkyne reagents, providing a straightforward and efficient access to chiral quaternary all-carbon centers bearing alkynyl groups.
CHINESE JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Jialin Qi, Fang Wei, Shuai Huang, Chen-Ho Tung, Zhenghu Xu
Summary: A new method has been developed for the synthesis of sulfur-containing chiral beta-lactams with two consecutive stereogenic centers using copper(I)-catalyzed asymmetric, three-component interrupted Kinugasa reaction. The key lies in the interception of in situ formed chiral four membered copper(I) enolate intermediate with sulfur electrophiles, resulting in good yields and excellent diastereo- and enantioselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Qinglin Zhang, Kang Liang, Chang Guo
Summary: A novel electrolytic system has been introduced to divert standard ionic reactivity, providing a brand-new pattern of reactivity-electricity-driven asymmetric catalysis, which serves as a privileged chiral platform for enantioselective radical allylation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Vladislav S. Kostromitin, Vitalij V. Levin, Alexander D. Dilman
Summary: This paper describes a method for performing radical difunctionalization of alkenes using fluorinated halides and nucleophilic components (thiolate and iodide anions). These nucleophilic fragments can act as redox active groups for subsequent transformations. The difunctionalization reaction involves photoredox generation of fluorinated radicals, their addition to the double bond, and copper-promoted C-S or C-I bond formation. The primary products can be further coupled with silyl enol ethers, alpha-(trifluoromethyl)styrenes, and trimethylsilyl cyanide to afford various fluorinated compounds.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Ze-Jun Xu, Xu-Yuan Liu, Ming-Zhu Zhu, Yu-Liang Xu, Yue Yu, Hai-Ruo Xu, Ai-Xia Cheng, Hong-Xiang Lou
Summary: In this study, two types of photoredox-catalyzed cascade reactions using diaryliodonium salts were developed for the concise synthesis of norascyronone A and beta-eudesmol. A rationally designed photoredox-catalyzed arylation/cyclization/Friedel-Crafts cascade reaction was used for the norascyronone synthesis, while a visible-light-induced radical cyclization/acyloxy-migration reaction was explored for the eudesmol synthesis, with mechanistic studies indicating initiation by one-electron oxidation of the enol ester.
Article
Chemistry, Multidisciplinary
Xiao-Long Su, Liu Ye, Ji-Jun Chen, Xiao-Dong Liu, Sheng-Peng Jiang, Fu-Li Wang, Lin Liu, Chang-Jiang Yang, Xiao-Yong Chang, Zhong-Liang Li, Qiang-Shuai Gu, Xin-Yuan Liu
Summary: The development of enantioconvergent cross-coupling of racemic alkyl halides with heteroarene C(sp(2))-H bonds has been achieved using a copper(I)/cinchona-alkaloid-derived N,N,P-ligand catalytic system, leading to high enantioselectivity of alpha-chiral alkylated heteroarenes, which show promise in drug discovery.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Xiao-Yang Dong, Tian-Ya Zhan, Sheng-Peng Jiang, Xiao-Dong Liu, Liu Ye, Zhong-Liang Li, Qiang-Shuai Gu, Xin-Yuan Liu
Summary: A copper-catalyzed asymmetric radical 1,4-carboalkynylation of 1,3-enynes has been reported, providing diverse synthetically challenging tetrasubstituted chiral allenes. The use of a chiral N,N,P-ligand is crucial for both reaction initiation and enantiocontrol over the highly reactive allenyl radicals. The reaction shows broad substrate scope and excellent functional group tolerance.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Multidisciplinary Sciences
Chi Zhang, Zhong-Liang Li, Qiang-Shuai Gu, Xin-Yuan Liu
Summary: In recent years, there has been a renaissance in the enantioselective functionalization of common C(sp(3))-H bonds through a radical pathway. The authors summarize the main achievements in the field, identifying two main reaction pathways determining the stereochemistry, and provide an outlook on future challenges and opportunities.
NATURE COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Jiao Yu, Ning-Yuan Yang, Jiang-Tao Cheng, Tian-Ya Zhan, Cheng Luan, Liu Ye, Qiang-Shuai Gu, Zhong-Liang Li, Guo-Qiang Chen, Xin-Yuan Liu
Summary: A copper-catalyzed radical 1,2-carbotrifluoromethylselenolation of alkenes was described, utilizing readily available alkyl halides and (Me4N)SeCF3 salt. The key to success lies in the use of a proline-based N,N,P-ligand to enhance copper's reducing capability, enabling the conversion of diverse alkyl halides to radicals through a single-electron transfer process. The reaction shows a broad substrate scope, including various mono-, di-, and trisubstituted alkenes with many functional groups.
Article
Chemistry, Inorganic & Nuclear
Zhuang Li, Xian-Yan Cheng, Ning-Yuan Yang, Ji-Jun Chen, Wen-Yue Tang, Jun-Qian Bian, Yong-Feng Cheng, Zhong-Liang Li, Qiang-Shuai Gu, Xin-Yuan Liu
Summary: A cobalt-catalyzed enantioconvergent radical Negishi C(sp(3))-C(sp(2)) cross-coupling has been developed, providing access to a range of enantioenriched 1,1-diarylmethanes with good yield and moderate enantioselectivities. Key to this discovery is the use of a chiral multidentate anionic N,N,P-ligand to coordinate with the cobalt catalyst and control the chiral environment.
Article
Chemistry, Organic
Xiao-Long Su, Sheng-Peng Jiang, Liu Ye, Guo-Xing Xu, Ji-Jun Chen, Qiang-Shuai Gu, Zhong-Liang Li, Xin-Yuan Liu
Summary: A new copper-catalyzed C(sp(3))-C(sp(2)) cross-coupling reaction has been developed for the synthesis of pharmaceutically useful compounds. The key to success lies in the use of a proline-based ligand to enhance the reducing capability of copper, allowing the conversion of benzyl bromides to radical species under ambient conditions. The reaction shows excellent functional group tolerance and a broad substrate scope.
Article
Chemistry, Multidisciplinary
Yu-Feng Zhang, Xiao-Yang Dong, Jiang-Tao Cheng, Ning-Yuan Yang, Li-Lei Wang, Fu-Li Wang, Cheng Luan, Juan Liu, Zhong-Liang Li, Qiang-Shuai Gu, Xin-Yuan Liu
Summary: This study demonstrates the successful use of sulfoximines as ammonia surrogates for enantioconvergent radical C-N coupling with diverse racemic secondary alkyl halides, achieving high yields and enantioselectivity. The obtained alpha-chiral primary amines can be converted to various synthetic building blocks, ligands, and drugs, highlighting the potential of enantioconvergent radical cross-coupling as a general chiral carbon-heteroatom formation strategy.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Physical
Huan Zhou, Zhong-Liang Li, Qiang-Shuai Gu, Xin-Yuan Liu
Summary: Transition-metal-catalyzed asymmetric C-(sp(3))-C cross-coupling is an efficient method for the rapid synthesis of enantioenriched molecules. Chiral copper catalysts have been designed to promote a variety of asymmetric radical C(sp(3))-C cross-coupling reactions with high efficiency and enantioselectivity. The key to success lies in the design of chiral ligands to initiate the reaction and achieve enantiocontrol over the highly reactive prochiral alkyl radical species.
Article
Chemistry, Organic
Na Wang, Li-Wen Fan, Jin Zhang, Qiang-Shuai Gu, Jin-Shun Lin, Guo-Qiang Chen, Xin-Yuan Liu, Peiyuan Yu
Summary: This study investigates the highly enantioselective intramolecular hydroamination reaction and uncovers its uncommon reaction mechanism. The reactivity of this reaction is primarily determined by the substituents on the internal carbon of the alkene, as well as the substituents on the terminal alkene carbons. The lower acidity of chiral phosphoric acids compared to chiral NTPAs results in a slower reaction.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Wu Yang, Lin Liu, Jiandong Guo, Shou-Guo Wang, Jia-Yong Zhang, Li-Wen Fan, Yu Tian, Li-Lei Wang, Cheng Luan, Zhong-Liang Li, Chuan He, Xiaotai Wang, Qiang-Shuai Gu, Xin-Yuan Liu
Summary: In this study, a strategy for catalytic enantioselective hydroxylation of prochiral dihydrosilanes is described. The reaction provides Si-chiral silanols with high enantioselectivity and excellent functional group compatibility. Furthermore, the obtained products exhibit high structural diversity and can be further transformed using established synthetic schemes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Peng-Fei Wang, Jiao Yu, Kai-Xin Guo, Sheng-Peng Jiang, Ji-Jun Chen, Qiang-Shuai Gu, Ji-Ren Liu, Xin Hong, Zhong-Liang Li, Xin-Yuan Liu
Summary: In this study, a copper/chiral N,N,N-ligand catalytic system was developed for the enantioconvergent cross-coupling of benzyl/propargyl halides with alkenylboronate esters, providing enantiocontrol over highly reactive alkyl radicals.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Fu-Li Wang, Chang-Jiang Yang, Ji-Ren Liu, Ning-Yuan Yang, Xiao-Yang Dong, Ruo-Qi Jiang, Xiao-Yong Chang, Zhong-Liang Li, Guo-Xiong Xu, Dai-Lei Yuan, Yu-Shuai Zhang, Qiang-Shuai Gu, Xin Hong, Xin-Yuan Liu
Summary: In contrast to the well-established enantioconvergent radical C(sp(3))-C cross-coupling, the coupling of tertiary electrophiles to forge all-carbon quaternary stereocentres remains unexplored. Here, we demonstrate a general copper-catalysed enantioconvergent C(sp(3))-C(sp) cross-coupling using rational design of chiral ligands. This protocol provides a practical platform for the construction of chiral carbon building blocks of interest in organic synthesis.
Article
Chemistry, Organic
Jun-Bin Tang, Jun-Qian Bian, Yu-Shuai Zhang, Yong-Feng Cheng, Han-Tao Wen, Zhang-Long Yu, Zhong-Liang Li, Qiang-Shuai Gu, Guo-Qiang Chen, Xin-Yuan Liu
Summary: A copper-catalyzed highly anti-selective radical 1,2-alkylarylation of terminal alkynes has been established, providing facile access to various stereo-defined trisubstituted alkenes in high yield under mild reaction conditions.
Article
Chemistry, Multidisciplinary
Xiao-Yang Dong, Zhong-Liang Li, Qiang-Shuai Gu, Xin-Yuan Liu
Summary: This article mainly introduces the research progress on enantioconvergent radical cross-coupling reactions. Compared with chiral nickel catalysts, the study of copper-catalyzed enantioconvergent radical cross-coupling is less explored, primarily due to the weak reducing capability of copper. In recent years, researchers have been dedicated to developing chiral ligands for copper-catalyzed enantioconvergent radical cross-coupling to address the issues of enantiocontrol and reaction initiation speed.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Xian-Yan Cheng, Yu-Feng Zhang, Jia-Huan Wang, Qiang-Shuai Gu, Zhong-Liang Li, Xin-Yuan Liu
Summary: This paper presents a copper-catalyzed enantioselective intermolecular radical 1,2-carboamination reaction using readily accessible alkyl halides and alkenes. The success of this method is attributed to the conceptual design of a counterion/highly sterically demanded ligand coeffect, which promotes the ligand exchange and formation of chiral C-N bonds. The reaction is versatile and delivers various chiral amine building blocks of interest in organic synthesis.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)