Article
Chemistry, Multidisciplinary
Guanjie Wang, Juhui Huang, Linxue Zhang, Jinna Han, Xiaoxiang Zhang, Jie Huang, Zhenqian Fu, Wei Huang
Summary: Axially chiral molecules are widely used in various fields of chemistry, and the synthesis of axially chiral molecules catalyzed by NHCs remains underdeveloped. In this study, we successfully achieved the atroposelective synthesis of axially chiral heteroaryl-aryls using chiral NHCs as catalysts for highly enantioselective Coates-Claisen rearrangements via catalytically generated alpha, beta-unsaturated acyl azoliums. This approach enables the concise synthesis of tetra-ortho-substituted 2-pyrones with good yield and chirality control.
SCIENCE CHINA-CHEMISTRY
(2022)
Article
Chemistry, Organic
Yuxing Cai, Jiean Chen, Yong Huang
Summary: This report describes a successful organocatalytic 1,4-alkylacylation of 1,3-enynes using a ketyl radical generated from single-electron oxidation of the Breslow intermediate as a coupling partner of allenyl radicals. The transformation exhibited remarkable tolerance to both aromatic and radical precursors.
Article
Chemistry, Multidisciplinary
Jian Song, Wen-Hua Zheng
Summary: Despite the widespread use of boronic acids in catalysis, the development of efficient chiral boronic acids remains challenging. In this study, a rational design and a concise synthesis of new C2-symmetric disubstituted boronic acids, or borinic acids, were disclosed. These chiral borinic acids were found to be effective in achieving highly enantioselective desymmetrization of 2,2-disubstituted-1,3-propanediols, leading to chiral diols with a quaternary stereocenter. A range of substrates were successfully utilized in this reaction, providing chiral diols with high enantioselectivity. 11B NMR studies confirmed the presence of tetracoordinate borinate in the catalytic cycle, and a stereocontrol model was proposed.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Wei Zhao, Jing Liu, Xiangkui He, Hao Jiang, Liangqiu Lu, Wenjing Xiao
Summary: A NHC-catalyzed oxidative esterification reaction for synthesizing axially chiral aldehydes with mild conditions, excellent yields and enantioselectivity, broad substrate scope, and good functional group tolerance has been developed. It provides new possibilities for the synthesis of axially chiral aldehydes and their derivatives.
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Jiaming Wang, Changgui Zhao, Jian Wang
Summary: Axial chirality is widely present in natural products and pharmaceutical compounds, and recent advances in using NHC organocatalysts have opened up new opportunities for the synthesis of enantioenriched axially chiral molecules. This perspective highlights the importance of NHCs in catalyzing the synthesis of axially chiral scaffolds and serves as a stepping stone for future investigations in this area.
Article
Chemistry, Organic
Yunpeng Chu, Fang Hu, Peng Feng, Xin-Ping Hui
Summary: The first N-heterocyclic carbene-catalyzed enantioselective dearomatizing annulation of benzoxazoles with alpha,beta-unsaturated aldehydes has been achieved, resulting in moderate to good yields and moderate to excellent enantioselectivities.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Physical
Yoshinori Hashimoto, Shingo Harada, Ryosuke Kato, Kotaro Ikeda, Jannis Nonnhoff, Harald Groeger, Tetsuhiro Nemoto
Summary: This study reported a catalytic approach for the formal synthesis of more than 20 types of sarpagine/macroline alkaloids, with two key steps being the amide insertion reaction using cheap copper and biocatalytic asymmetric desymmetrization.
Article
Chemistry, Multidisciplinary
Ludwig Zapf, Udo Radius, Maik Finze
Summary: The paper describes the synthesis of 1,3-bis(tricyanoborane)imidazolate anion and its derivatives, including a novel dianionic N-heterocyclic carbene. These compounds exhibit unique electronic and steric properties, making them promising ligands and building blocks for coordination chemistry.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Applied
Jen-Yu Kuan, I-Ting Chen, Hsuan Lin, Jeng-Liang Han
Summary: We have developed a substrate-dependent, regio- and stereocontrolled diversity-oriented organocatalytic vinylogous Michael addition/cyclization cascade of 2-alkylidene indane-1,3-diones with enals, using secondary amines as the catalyst. This method allows for the selective synthesis of spiroindane-1,3-diones, tetrahydrofluoren-9-one derivatives, and benzofused oxabicyclo[3.3.1]nonanes. Plausible catalytic pathways have been proposed, and DFT calculations have clarified the mechanisms involved.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Bang-An Zhou, Xue-Ning Li, Chun-Lin Zhang, Zhi-Xiang Wang, Song Ye
Summary: The N-heterocyclic carbene-catalyzed enantioselective synthesis of axially chiral diaryl ethers via desymmetrization of prochiral 2-aryloxyisophthalaldehydes has been presented. This method exhibits mild reaction conditions, broad substrate scope, and excellent enantioselectivity. The utility of this methodology has been demonstrated through late-stage functionalization and various enantioretentive transformations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Jan Sietmann, Mike Ong, Christian Mueck-Lichtenfeld, Constantin G. Daniliuc, Johannes M. Wahl
Summary: Asymmetric access to gamma-lactams was achieved using (1S,2R)-1-amino-2-indanol for chiral induction, with downstream stereoinduction up to 88:12 dr. Mechanistic analysis revealed a Curtin-Hammett scenario, supported by spectroscopic, crystallographic, and computational studies. The method allows for the synthesis of optically pure gamma-lactams, including those with all-carbon quaternary stereocenters, and is exemplified by the formal synthesis of drug molecules baclofen, brivaracetam, and pregabalin.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Multidisciplinary
Rajendra S. Ghadwal
Summary: This review article aims to highlight recent advances in accessing stable iMICs, quantifying their properties, and exploring their applications in synthesis and catalysis. The synthetic viability and use of vicinal C4,C5-anionic dicarbenes (ADCs) based on a 1,3-imidazole framework are also presented. iMICs and ADCs have the potential to push the limit of classical NHCs by enabling access to conceptually new main-group heterocycles, radicals, molecular catalysts, ligand sets, and more.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Multidisciplinary
Yi Zhang, Hui Cai, Xiuhai Gan, Zhichao Jin
Summary: This paper provides a systematic review of N-heterocyclic carbene-catalyzed enantioselective kinetic resolutions, dynamic kinetic resolutions, and desymmetrization reactions. The content is organized based on the activation modes involved in these transformations. Future advances in this highly active research field are also discussed from the authors' perspectives.
SCIENCE CHINA-CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Tsubasa Inokuma, Kentaro Hashimoto, Tatsuya Fujiwara, Chunzhao Sun, Satoru Kuwano, Ken-ichi Yamada
Summary: The remote electronic effect of a chiral aminoindanol-derived N-heterocyclic carbene catalyst on an asymmetric benzoin reaction was investigated. The catalyst containing remote electron-withdrawing substituents increased the enantioselectivity of the reaction, albeit at the expense of the reaction rate. DFT calculations provided a rationale for the enhanced enantioselectivity.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Multidisciplinary Sciences
Jia-Lei Yan, Rakesh Maiti, Shi-Chao Ren, Weiyi Tian, Tingting Li, Jun Xu, Bivas Mondal, Zhichao Jin, Yonggui Robin Chi
Summary: In this study, a chiral solution utilizing N-heterocyclic carbene (NHC) catalyst was developed for the preparation of axially chiral styrenes with high enantioselectivity and excellent yields. The sulfone and carboxylic ester moieties in the styrenes are common functional groups in bioactive molecules and asymmetric catalysis.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Jun-Qi Zhang, Yunkui Liu, Xing-Wang Wang, Liming Zhang
Article
Chemistry, Physical
Jun-Bo Chen, Man Xu, Jun-Qi Zhang, Bing-Bing Sun, Jia-Ming Hu, Jie-Qiang Yu, Xing-Wang Wang, Yuanzhi Xia, Zheng Wang
Article
Chemistry, Organic
Wei-Tai Fan, Xiao-Peng Yang, Hao-Peng Lv, Xing-Wang Wang, Zheng Wang
Article
Chemistry, Organic
Hao-Peng Lv, Xiao-Peng Yang, Bai-Lin Wang, Hao-Di Yang, Xing-Wang Wang, Zheng Wang
Summary: An asymmetric [3 + 2] cycloaddition reaction has been developed for the synthesis of chiral multistereogenic vinyltetrahydrofurans using the Pd complex of a bidentate phosphoramidite (Me-BIPAM) as the catalyst. The reaction provides a wide variety of products in good yields with excellent diastereo- and enantioselectivities (up to >20:1 dr, 99% ee).
Article
Chemistry, Applied
Hao-Di Yang, Jun-Bo Chen, Cheng Peng, Wen-Kai Liu, Sheng-Suo Zhou, Jia-Xin Song, Zheng-Hang Qi, Yong Wang, Xing-Wang Wang
Summary: Chiral bis-oxalamide/rare-earth metal complexes catalyze the asymmetric inverse-electron-demand oxa-hetero-Diels-Alder reactions. The reactions produce optically active functionalized dihydropyran compounds with high diastereo- and enantioselectivity. The coordination mode of chiral bis-oxalamide with Sc(III) and the regio- and stereocontrol were investigated.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Wen-Kai Liu, Bai-Lin Wang, Sheng-Suo Zhou, Jun-Hao Shen, Zheng Wang, Xing-Wang Wang
Summary: An asymmetric linear selective allylic alkylation of vinylaziridines with 3-aryl oxindoles has been achieved using a chiral oxamide-phosphine/palladium complex in methanol. This reaction provides a wide range of 3,3-disubstituted oxindole derivatives with excellent regio- and enantioselectivities.
Article
Chemistry, Applied
Jun-Hao Shen, Sheng-Suo Zhou, Bai-Lin Wang, Wen-Kai Liu, Zheng Wang, Xing-Wang Wang
Summary: The Pd-catalyzed enantioselective linear-allylic alkylation of vinyl benzoxazinanones with 3-substituted oxindoles was achieved using a chiral oxamide-phosphine ligand (COAP-Bn) under mild reaction conditions. The method provided a series of optically active 3,3'-disubstituted oxindole derivatives with a quaternary stereogenic center and a linear aryl amino side chain in good yields (55-98%) and high enantioselectivity (96-99% ee) for 3-(hetero)aryl substituted oxindoles. The COAP ligands demonstrated their capacity to construct diverse chiral 3,3-disubstituted oxindole compounds with various quaternary stereogenic centers.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Jun -Bo Chen, Wen -Kai Liu, Jia-Xin Song, Zheng Wang, Xing-Wang Wang
Summary: A one-pot, five-step domino reaction was developed to synthesize a series of chiral bis-oxalamide palladium(II) complexes with tetraaryl-conjugated substituents in good yields. These complexes exhibited noticeable blue fluorescence under ultraviolet light irradiation.
Article
Chemistry, Organic
Sheng-Suo Zhou, Jun-Hao Shen, Wen-Kai Liu, Xing-Yun Sun, Jia-Yu Song, Zheng Wang, Zheng-Hang Qi, Xing-Wang Wang
Summary: A chiral oxalamide phosphine (COAP)-Pd-catalyzed asymmetric cascade formal [4 + 1] annulation was developed between racemic vinyl benzoxazinones and N-tosylhydrazone sodium salts. The corresponding trans-2,3-disubstituted indoline products with contiguous stereogenic centers were obtained in good yields with high diastereo- and enantioselectivity. The catalytic outcomes and computational DFT study showed that the biphilic transformation proceeded by a dynamic kinetic asymmetric transformation (DYKAT) process. The enantio-determining step is a stereoselective migratory insertion of Pd(ii)-carbene into a pendant chiral p-allylpalladium-COAP complex, followed by reductive elimination to fulfill the annulation.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Jun-Bo Chen, Cheng Peng, Sheng-Suo Zhou, Yong Wang, Zheng Wang, Xing-Wang Wang
Summary: A novel chiral ligand, COAP, was developed for the palladium-catalyzed asymmetric allylic amination, providing enantiomerically enriched compounds in high yields and high enantioselectivities. Mechanistic studies revealed the crucial role of carbonyl coordination in the regio- and enantioselective control of the reaction. The COAP ligand possesses modular structure, fine stereoelectronic tunability, and easy synthesis.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Xiao-Peng Yang, Hao-Peng Lv, Hao-Di Yang, Bai-Lin Wang, Xing-Wang Wang
Summary: Enantioselective copper-catalyzed cascade inter- and intramolecular amidation was achieved between ethynyl benzoxazinanones and alpha-halohydroxamates in the presence of an indapybox ligand. A series of exo-methylene 3-aminoindoline derivatives were obtained in good yields with high enantioselectivities under mild reaction conditions.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Organic
Nai-Kai Li, Bing-Bing Sun, Jun-Bo Chen, Hao-Di Yang, Bai-Lin Wang, Jie-Qiang Yu, Xing-Wang Wang, Zheng Wang
Summary: This paper demonstrates the asymmetric catalytic synthesis of three series of spirooxindole-pyran derivatives via an inverse-electron-demand oxa-hetero-Diels-Alder reaction. The reactions were carried out with chiral bisoxazoline/copper(ii) complexes as Lewis acid catalysts, resulting in excellent yields with high diastereo- and enantioselectivities under mild reaction conditions.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Organic
Bing-Bing Sun, Jun-Bo Chen, Jun-Qi Zhang, Xiao-Peng Yang, Hao-Peng Lv, Zheng Wang, Xing-Wang Wang
ORGANIC CHEMISTRY FRONTIERS
(2020)
Article
Chemistry, Organic
Bing-Bing Sun, Jun-Qi Zhang, Jun-Bo Chen, Wei-Tai Fan, Jie-Qiang Yu, Jia-Ming Hu, Xing-Wang Wang
ORGANIC CHEMISTRY FRONTIERS
(2019)
