Article
Chemistry, Organic
Yadi Niu, Laiping Yao, Hongli Zhao, Xue Tang, Qian Zhao, Yuling Wu, Bo Han, Wei Huang, Gu Zhan
Summary: This study presents a new method for the asymmetric synthesis of spiroxindole cyclopentanes containing five stereocenters. The strategy demonstrated a broad substrate scope and high selectivity.
Article
Chemistry, Organic
Sayan Shee, Soumen Barik, Arghya Ghosh, Akkattu T. Biju
Summary: This study describes a method for the facile synthesis of functionalized dihydrocoumarins catalyzed by N-heterocyclic carbene (NHC), in which initially formed NHC-homoenolates undergo a specific reaction pathway to yield the products. Preliminary studies indicate that the homoenolate pathway may be more favorable than other intermediates for product formation.
Article
Chemistry, Multidisciplinary
Arghya Ghosh, Shilpa Barik, Sayan Shee, Akkattu T. Biju
Summary: The NHC-catalyzed cascade reaction allows for the enantioselective synthesis of tetra-substituted tetralines and tetrahydro indolizines from enals and beta-(hetero)aryl enones. The catalytically generated chiral alpha,beta-unsaturated acylazoliums from enals under oxidative conditions reacted in a Michael-Michael-lactonization sequence to form tricyclic delta-lactone products with four contiguous stereocentres.
CHEMICAL COMMUNICATIONS
(2021)
Review
Chemistry, Multidisciplinary
Runjiang Song, Zhichao Jin, Yonggui Robin Chi
Summary: This review evaluates and summarizes the covalent activation of heteroatoms enabled by N-heterocyclic carbene (NHC) organic catalysts for enantioselective reactions. Sulfur, oxygen, and nitrogen atoms can be activated in this manner to construct chiral carbon-heteroatom bonds with high optical enantioselectivities. The key lies in the formation of intermediates covalently bound to the NHC catalyst, in which the heteroatom of the substrate is activated as a nucleophilic reactive site.
Article
Chemistry, Organic
Yingling Nong, Chen Pang, Kunpeng Teng, Sheng Zhang, Qian Liu
Summary: An N-heterocyclic carbene (NHC)-catalyzed chemoselective activation reaction of 1-cyclopropylcarbaldehydes and a-alkynyl enals is reported. The reaction proceeds via NHC catalysis of 1-cyclopropylaldehydes, followed by a [2 + 4] cycloaddition reaction with a-alkynyl enals. Dihydropyranone derivatives with different substituents and substitution patterns are obtained in good to excellent yields with excellent enantio- and diastereoselectivities under mild conditions.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Jianfeng Jiang, Xia Wang, Shengping Liu, Sichen Zhang, Binmiao Yang, Yu Zhao, Shenci Lu
Summary: We report an unprecedented gold and oxidative NHC relay catalysis for highly enantioselective cascade annulation between readily available alpha-amino-ynones with enals. This method utilizes in situ-generated pyrrolin-4-ones as a novel and versatile synthon, reacting with alpha,beta-unsaturated acylazolium intermediates generated from enals by oxidative NHC catalysis to produce pyrrole-fused lactones in high yield and excellent enantioselectivity. The utility of the lactone products is demonstrated by their facile conversion to densely functionalized pyrroles and pyrrolin-4-ones with high yields and excellent stereopurity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Yan Li, Zhilin Li, Zhiqiang Zhang
Summary: The mechanism and stereoselectivity of the NHC-catalyzed [3+4] annulation reaction were investigated using DFT calculations. The results showed that the C-C bond formation step is decisive for stereoselectivity, with the RS-configurational isomer being the main product. Non-covalent interactions play a crucial role in determining the stereochemistry of the reaction.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Organic
Zhan-Yong Wang, Fumin Shen, Ting Yang, Jun-Kai Zhang, Rongxiang Chen, Kai-Kai Wang, Hongxin Liu
Summary: A novel method was developed for the construction of medicinally important spirobenzofuranone derivatives using an NHC mediated three-component cascade reaction with mild reaction conditions. The reaction generates three consecutive stereocenters, including an all-carbon substitution, and can accommodate various substituents and substitution patterns, affording the products in moderate to good yields with excellent diastereoselectivities and moderate enantioselectivity.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Shuang-Liang Liu, Yan Qiao, Yang Wang
Summary: A general mechanistic map has been proposed and studied for NHC-catalyzed transformation reactions of saturated carboxylic anhydrides, predicting the origin of chemo- and stereo-selectivities. The fundamental pathway of this reaction includes processes such as C-O bond cleavage, alpha-H elimination, beta-H elimination, functionalization with benzylidene diketone, acyl migration, aldol addition, catalyst dissociation, and decarboxylation. The chemoselectivities in other pathways and the stereoselectivity-determining step have also been investigated.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Yan Li, Mingchao Zhang, Zhiqiang Zhang
Summary: A systematic computational study was performed to disclose the reaction mechanism and selectivity in the NHC-catalyzed reaction of 2-bromoenal and 6-methyluracil-5-carbaldehyde. The catalytic cycle was found to consist of eight elementary steps, with the Bronsted acid playing a crucial role in proton transfer and decarboxylation. Addition to 6-methyluracil-5-carbaldehyde was identified as the determining factor for chemo- and stereoselectivity, with CH...N, CH...p, and LP...p interactions influencing the stereoselectivity.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Ketema Alemayehu Asserese, Hanmin Huang
Summary: A novel palladium-catalyzed cascade hydrocarbonylation followed by intramolecular spirolactonization of 2-vinylaryl hydroxyalkyl ketones has been developed, providing high yields and high chemoselectivities of oxaspirolactones. This method is compatible with various functional groups and uses commercially available catalyst components under mild reaction conditions.
Article
Chemistry, Organic
Guihua Nie, Tingting Li
Summary: This article summarizes the facile syntheses of multicyclic molecules through multi-step cascade reactions with N-Heterocyclic carbene (NHC)-catalyzed LUMO activation strategies. The reaction mechanisms involved in these cascade catalytic transformations are also provided and discussed. The review article is arranged according to the reaction starting materials that are used for the NHC-catalytic activation processes.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Lingchen He, Ebrahim-Alkhalil M. A. Ahmed, Hongxin Liu, Xingen Hu, Hong-Ping Xiao, Juan Li, Jun Jiang
Summary: In this study, a Ni-bidentate oxazoline catalyzed highly enantio- and diastereoselective decarboxylative aldol reaction was described, yielding alpha-substituted beta-hydroxy butyrolactones and dihydrocoumarins with an all-carbon quaternary stereocenter. Successful transformations of the products into an aliphatic tertiary alcohol and a multi-substituted 1,4-diol were also achieved. This research has significant theoretical and practical implications.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Hai-Bin Yang, Xiao-Fang Jin, Hui-Ying Jiang, Wenwei Luo
Summary: A C(sp2)-C(sp2) bond was formed through a photoredox/N-heterocyclic carbene (NHC)-catalyzed radical cross-coupling reaction, presenting an alternative approach to traditional electron pair processes. This method demonstrated the first example of an NHC-catalyzed two-component radical cross-coupling reaction involving C(sp2)-centered radical species. The decarboxylative acylation of oxamic acid with acyl fluoride proceeded under mild conditions, enabling the synthesis of various useful alpha-keto amides, including sterically congested compounds.
Article
Chemistry, Organic
Tian-Yu Zhang, Yong Wu, Shuai Liu, Jing-Qi Tao, Xu Yang, Xue-Qi Wang, Xin-Hua Duan, Li-Na Guo
Summary: An inexpensive iron-catalyzed alkoxylradical-induced C-C bond cleavage/gem-difluoroalkylation cascade is developed. Fluorinated distal diketones are synthesized via a ring-opening strategy regulated by the structure of alkoxyl radical precursors, while difluoroalkylated medium-sized lactones and macrolactones are constructed through a ring-expansion strategy. Both protocols show mild and redox neutral conditions, broad substrate scope, and good functional group compatibility.
Article
Chemistry, Multidisciplinary
Tingting Li, Chengli Mou, Puying Qi, Xiaolin Peng, Shichun Jiang, Gefei Hao, Wei Xue, Song Yang, Lin Hao, Yonggui Robin Chi, Zhichao Jin
Summary: A catalytic atroposelective cycloaddition reaction between thioureas and ynals has been developed, enabling the establishment of C-N axial chirality with excellent optical purities. The resulting axially chiral thiazine derivative products contain multiple functional groups and are suitable for further transformations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Multidisciplinary
Tingting Li, Zhichao Jin, Yonggui Robin Chi
Summary: This review discusses N-heterocyclic carbene-catalyzed reactions for the formation of aromatic compounds, categorizing them into 4 types based on activation modes. The achievements, challenges, and future research directions in NHC-catalyzed arene construction processes are summarized. The outlook is based on the authors' opinions and knowledge on the trends of NHC organocatalysis development.
SCIENCE CHINA-CHEMISTRY
(2022)
Article
Chemistry, Physical
Xiaokang Lv, Jun Xu, Cuiyun Sun, Fen Su, Yuanlin Cai, Zhichao Jin, Yonggui Robin Chi
Summary: Ferrocene-derived dicarbaldehydes with pro-chiral planes can be desymmetrized under the catalysis of chiral Nheterocyclic carbene organic catalysts, resulting in enantiomerically enriched planar chiral ferrocene products. The reaction selectively activates and reacts with one aldehyde moiety while leaving the other untouched. The obtained products show potential applications as catalysts in chemical synthesis and for antimicrobial activities in pesticide development.
Review
Agriculture, Multidisciplinary
Zhiguo Zheng, Ali Dai, Zhichao Jin, Yonggui Robin Chi, Jian Wu
Summary: This review summarizes the research progress and design principles of pesticides containing TFMP fragments, aiming to provide a convenient reference for graduate students with educational value.
JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY
(2022)
Article
Agriculture, Multidisciplinary
Yanlin Chen, Tingting Li, Zhichao Jin, Yonggui Robin Chi
Summary: A new class of axially chiral thiazine molecules were constructed and showed promising antibacterial activities against Xanthomonas oryzae pv. oryzae (Xoo). The axial chiralities of these compounds had clear impacts on the inhibitory activities against Xoo. The optimal molecule exhibited superior inhibitory activity and outperformed the controls in in vivo studies.
JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Rui Deng, Shuquan Wu, Chengli Mou, Jianjian Liu, Pengcheng Zheng, Xinglong Zhang, Yonggui Robin Chi
Summary: A novel carbene-catalyzed sulfonylation reaction between enone aryl aldehydes and sulfonyl chlorides has been disclosed, leading to the efficient installation of sulfone moieties. The NHC catalyst provides activation and stereoselectivity control on a very remote site of the enone aryl aldehyde substrates. Water plays a crucial role in modulating catalyst deactivation and reactivation routes involving reactions between NHC and sulfonyl chloride.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Multidisciplinary Sciences
Shi-Chao Ren, Xing Yang, Bivas Mondal, Chengli Mou, Weiyi Tian, Zhichao Jin, Yonggui Robin Chi
Summary: This study reports a decarboxylative radical coupling of carboxylic acids and acyl imidazoles catalyzed by an N-heterocyclic carbene and photocatalyst. The carboxylic acids serve as direct radical precursors, and suitable acyl imidazoles can also be generated in situby a reaction with CDI. The method is extended to three-component coupling by using alkenes as a third coupling partner via a radical relay process. The mild reaction conditions, simplicity, and use of easily available starting materials make this method a powerful strategy for constructing complex ketones and modifying natural products and medicines.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Wen-Xin Lv, Hang Chen, Xinglong Zhang, Chang Chin Ho, Yingguo Liu, Shuquan Wu, Haiqi Wang, Zhichao Jin, Yonggui Robin Chi
Summary: Chemical synthesis or modification of saccharides is difficult due to the challenge of site-selective reactions on their similar hydroxyl groups. The lack of efficient tools hinders the understanding of saccharide-related biological processes and the development of saccharide-based pharmaceuticals. In this study, a programmable multilayered selectivity-amplification strategy using boronic acids and N-heterocyclic carbene (NHC) catalysts is presented for site-specific acylation of monoglycosides.
Article
Chemistry, Multidisciplinary
Chenghao Tang, Wei Wang, Guoyong Luo, Chaoyang Song, Zhaowei Bao, Pei Li, Gefei Hao, Yonggui Robin Chi, Zhichao Jin
Summary: The first carbene-catalyzed asymmetric chemoselective cross silyl benzoin reaction has been developed, which can efficiently synthesize alpha-silyloxy ketones with excellent optical purities. The reaction mechanism of this cross Brook-Benzoin reaction has been investigated, and the obtained ketone derivatives show promising agrochemically interesting activity against harmful plant bacteria.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Organic
Hongling Wang, Yonggui Robin Chi, Xuan Huang
Summary: N-heterocyclic carbene (NHC) catalysis is a versatile strategy for building molecules, and has been studied in combination with other catalytic agents to enhance reactivity and yield.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Multidisciplinary Sciences
Jianjian Liu, Mali Zhou, Rui Deng, Pengcheng Zheng, Yonggui Robin Chi
Summary: The authors report a synthetic method for the asymmetric synthesis of chiral sulfoxides using intramolecular chalcogen bonding interactions. The reaction involves conformational locking and facile isomerization enabled by chalcogen bonding interactions, leading to the formation of chiral sulfoxide products with excellent optical purities.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Mali Zhou, Jianjian Liu, Rui Deng, Qingyun Wang, Shuquan Wu, Pengcheng Zheng, Yonggui Robin Chi
Summary: A catalytic strategy for asymmetric synthesis of chiral tetrasubstituted silicon-stereogenic silanes is disclosed. By using a covalently symmetric silane as the substrate and a N-heterocyclic carbene catalyst, the substrate can be selectively activated and undergo desymmetrization reaction to afford optically enriched products.
Article
Chemistry, Multidisciplinary
Xing Yang, Liwen Wei, Yuelin Wu, Liejin Zhou, Xinglong Zhang, Yonggui Robin Chi
Summary: In this study, a novel bridged biaryl containing medium-sized rings was selectively synthesized via N-heterocyclic carbene organocatalysis. The reaction began with the addition of the carbene catalyst to the aminophenol-derived aldimine substrate, followed by oxidation and intramolecular desymmetrization to form 1,3-oxazepine-containing bridged biaryls with high yields and excellent enantioselectivities. These products can be readily transformed into chiral phosphite ligands.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Jie Lv, Zhichao Jin, Hongling Wang, Yonggui Robin Chi
Summary: This review systematically summarizes the carbon-sulfur (C-S) bond formation reactions enabled by N-heterocyclic carbene (NHC) organocatalysis, including S-esterification, nucleophilic S-conjugate addition, S-addition reactions with electrophiles, and C-S bond formations via cooperative NHC/transition metal-catalyzed radical reactions. The review also provides the authors' own comprehension and perspectives on this highly active research field.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2022)
Article
Chemistry, Organic
Rakesh Maiti, Jun Xu, Jia-Lei Yan, Bivas Mondal, Xing Yang, Huifang Chai, Lin Hao, Zhichao Jin, Yonggui Robin Chi
Summary: A carbene-catalyzed addition reaction between isothioureas and enals under oxidative conditions has been reported, resulting in the formation of two carbon-nitrogen bonds in a highly regio-selective manner. Various sulphur-containing 5,6-dihydropyrimidin-4-ones have been obtained with high optical purity.
ORGANIC CHEMISTRY FRONTIERS
(2021)
