Article
Chemistry, Organic
Eiji Tayama, Goshu Shimizu, Ryo Nakao
Summary: The base-induced Sommelet-Hauser rearrangement of various types of N-(pyridinylmethyl) tet-raalkylammonium salts was investigated, and N,N-dialkyl-alpha-pyridinylamino acid esters were obtained. Through a series of experimental conditions, the target product was successfully synthesized, and the method was found to be efficient, simple, and mild.
Article
Chemistry, Organic
Dengyang Zhao, Yingjie Pan, Shengkun Guo, Xiaoyun Chen, Hong Hou, Ying Han, Chaoguo Yan, Yaocheng Shi, Shaoqun Zhu
Summary: This study describes a copper-catalyzed efficient oxidative dearomatized functionalization of indoles using alcohols as nucleophiles. Various 3-alkoxy-2-oxindoles were synthesized with good isolated yields. The synthetic potential of the reaction was demonstrated through large-scale reactions and derivatization of the desired products.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Krishna Kumar, Bhuvnesh Singh, Soumyadip Hore, Ravi P. Singh
Summary: A novel catalytic system has been developed for the direct enantioselective vinylogous aldol reaction between 3-alkylidene-2-oxindoles and pyrazole-4,5-diones. The bifunctional quinine-derived benzamide catalyst achieved highly functional rich pyrazolone moieties with excellent E/Z selectivity (>19:1) and high yields, as well as moderate enantioselectivity through H-bonding dual activation mode.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Di Tian, Zhuo-Chen Li, Ze-Hua Sun, Yu-Ping He, Li-Ping Xu, Hua Wu
Summary: This paper describes the first example of enantioselective catalytic Biltz synthesis that can selectively and regioselectively produce over 40 thiohydantoins with high stereocontrol, regardless of the symmetry of the thiourea structure. A one-pot synthesis of corresponding hydantoins is also demonstrated. Experimental studies and DFT calculations reveal the reaction pathway and origin of stereoselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Chenxiao Qian, Pengfei Li, Jianwei Sun
Summary: A catalytic enantioselective variant of oxidative rearrangement of indoles to access oxindoles has been developed using chiral phosphoric acid catalysis, providing a rapid access to a range of enantioenriched spirooxindoles with high enantioselectivity controlled by dynamic kinetic resolution.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
K. Naresh Babu, Souvik Pal, Arindam Khatua, Avishek Roy, Alakesh Bisai
Summary: The study demonstrated the catalytic asymmetric synthesis of 3-allyl-3'-aryl 2-oxindoles via the Pd(0)-catalyzed decarboxylative allylation of allylenol carbonates, providing access to a variety of 2-oxindole substrates with all-carbon quaternary stereocenters at the pseudobenzylic position (up to 94% ee) under additive-free and mild conditions. The synthetic potential of this method was highlighted by the asymmetric synthesis of the tetracyclic core of the alkaloid azonazine.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Organic
Cankun Luo, Zhiqian Lin, Yingdi Hao, Pengfei Jia, Ruizhi Lai, Li Guo, Yuan Yao, Yong Wu
Summary: A rhodium-catalyzed Sommelet-Hauser rearrangement using α-thioesters/α-selenoesters and sulfoxonium ylides has been developed for the synthesis of various sulfur/selenium-containing ortho-substituted aromatic compounds in medium to excellent yields. This reaction highlights the advantages of mild conditions and broad substrate scope.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Review
Chemistry, Multidisciplinary
Valentyn Pozhydaiev, Cyprien Muller, Joseph Moran, David Lebaeuf
Summary: beta-(Hetero)arylethylamines are extensively used in pharmaceuticals due to their broad range of biological activities, making them attractive targets for drug discovery. However, traditional synthesis methods often involve complex substrates, limiting the flexibility and diversity of compounds that can be accessed. To overcome these challenges, synthetic chemists have developed innovative and modular strategies to efficiently access beta-(hetero)arylethylamines, enabling the synthesis of more complex and selective molecules. This review highlights recent advancements in the synthesis of (hetero)arylethylamines and their significance in expanding the molecular complexity and practicality of drug development.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Inorganic & Nuclear
Lingyu Kong, Yajie Chou, Muriel Albalat, Marion Jean, Nicolas Vanthuyne, Stephane Humbel, Paola Nava, Herve Clavier
Summary: The concept of atropisomeric N-heterocyclic carbene (NHC)-metal complexes with C-2-symmetry was extended to palladium-based complexes. Through a comprehensive study of NHC precursors and screening of various NHC ligands, the formation of meso complexes was successfully circumvented. Eight atropisomeric NHC-palladium complexes were prepared and obtained with high enantiopurities through efficient chiral HPLC resolution. These complexes demonstrated good activity in the intramolecular alpha-arylation of amides, leading to the isolation of cyclic products with excellent enantioselectivities (up to 98% ee).
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Yihuo Liu, Siyu Ding, Mingli Xu, Jinli Xu, Dongping Cheng, Hong Wang, Xiaoliang Xu
Summary: A visible-light-promoted radical tandem reaction of N-arylsulfonyl-acrylamides with alpha-oxocarboxylic acids is reported, which undergoes decarboxylation, Smiles rearrangement, and intramolecular cyclization to afford a series of arylacylated oxindoles with potential pharmacological activities.
Article
Chemistry, Organic
Carlos Diez-Poza, Laura Fernandez-Pena, Paula Gonzalez-Andres, Asuncion Barbero
Summary: Developing new procedures with high stereoselectivity for synthesizing tetrahydropyrans is crucial for the synthesis of THP-containing natural products. In this study, we present an interesting protocol using silyl-Prins cyclization of vinylsilyl alcohols to synthesize polysubstituted halogenated tetrahydropyrans, where the Lewis acid type determines the reaction outcome. This methodology has been successfully applied to the synthesis of a known antinociceptive drug.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Yi Hou, Jiyou Huo, Ruoxin Li, Jun Hou, Pan Lei, Hongbo Wei, Weiqing Xie
Summary: A catalytic asymmetric nucleophilic reverse prenylation reaction was developed, using Ni-(II)/chiral N,N'-dioxide as the catalyst, to obtain good to excellent enantioselectivities in the reaction between 3-bromooxindoles and prenyltributylstannane. This reaction provides a convenient access to C3 reverse-prenylated oxindoles, enabling the asymmetric synthesis of debromoflustramine A in five steps.
Article
Chemistry, Organic
Freddy O. Rodriguez del Rey, Paul E. Floreancig
Summary: This manuscript describes a method in which Re2O7 in hexafluoroisopropyl alcohol converts alcohols into cationic intermediates through perrhenate esters, and discusses its application in the formation of weakly basic heterocyclic systems. The influence of the substrate structure on reaction rates and stereocontrol is also discussed.
Article
Chemistry, Multidisciplinary
Xu-Jie Wang, Huan-Huan Liu, Jun Kee Cheng, Shao-Hua Xiang, Bin Tan
Summary: A sulfur stereogenic center is important for pharmaceuticals and chiral auxiliaries. While methods for enantioselectively constructing sulfur stereocenters have been developed, the synthesis and isolation of S-stereogenic ylides has been elusive. We successfully developed the first catalytic enantioselective synthesis of sulfonium ylides with a chiral sulfur center, using judicious substrate design and a copper-catalyzed intramolecular carbene transfer reaction.
Article
Chemistry, Inorganic & Nuclear
Geanne M. R. Boston, Holger Butenschon
Summary: In this study, the first syntheses of triflate substituted cobaltocenium cations were reported. The reaction with triflic anhydride yielded the triflate substituted cobaltocenium cations, and further treatment with lithium diisopropylamide led to the first anionic thia-Fries rearrangements of cobaltocenium complexes.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Review
Chemistry, Multidisciplinary
Zhongxing Huang, Hee Nam Lim, Fanyang Mo, Michael C. Young, Guangbin Dong
CHEMICAL SOCIETY REVIEWS
(2015)
Article
Chemistry, Multidisciplinary
Yan Xu, Tianshun Su, Zhongxing Huang, Guangbin Dong
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2016)
Article
Chemistry, Multidisciplinary
Zhongxing Huang, Chengpeng Wang, Guangbin Dong
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2016)
Article
Chemistry, Organic
Zhongxing Huang, Guangbin Dong
Article
Chemistry, Physical
Zixi Zhu, Xinghan Li, Sicong Chen, Peng-hao Chen, Brent A. Billett, Zhongxing Huang, Guangbin Dong
Article
Multidisciplinary Sciences
Barry M. Trost, Zhongxing Huang, Ganesh M. Murhade
Article
Chemistry, Multidisciplinary
Barry M. Trost, Zhongxing Huang
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2019)
Article
Multidisciplinary Sciences
Barry M. Trost, Youliang Wang, Andreas K. Buckl, Zhongxing Huang, Minh H. Nguyen, Olesya Kuzmina
Article
Chemistry, Multidisciplinary
Pengwei Xu, Zhongxing Huang
Summary: A new method for desymmetrization using selective hydrosilylation of malonic esters has been developed to synthesize compounds with four stereocenters, offering a promising alternative to traditional desymmetric hydrolysis methods. The asymmetric reduction shows excellent enantioselectivity and chemoselectivity, capable of differentiating substituents and effectively synthesizing diverse stereocenters with distinct structural features.
Article
Chemistry, Multidisciplinary
Yin Zheng, Suihan Zhang, Kam-Hung Low, Weiwei Zi, Zhongxing Huang
Summary: This study reports a reductive desymmetrization of halomalonic esters using dinuclear zinc catalysts. The resulting α-halo-β-hydroxyesters serve as important intermediates for the synthesis of drug analogs and polyhalogenated monoterpenes.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Pengwei Xu, Shihao Liu, Zhongxing Huang
Summary: Desymmetrization of easily available disubstituted malonic esters is a rewarding strategy to access structurally diverse quaternary stereocenters. The asymmetric reduction of malonic esters generates functional groups with lower oxidation states, allowing for more chemoselective derivatization.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Pan Xu, Chang Shen, Aiqing Xu, Kam-Hung Low, Zhongxing Huang
Summary: In this study, a bifunctional catalyst prepared from dibutylmagnesium and a pipecolinol-derived tetradentate ligand was found to enable the diastereo- and enantioselective construction of vicinal stereocenters from easily available starting materials. The high stereoselectivity was attributed to the rigid conformation of the diketone in the catalyst pocket, where the Lewis acidic magnesium center and the free hydroxyl group bind with both carbonyls.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Zhongxing Huang
Summary: Asymmetric cyanosilylation is an important tool for converting readily available ketones into cyanohydrins with diverse reactivity. While a large number of studies have been conducted on the cyanosilylation of monoketones, particularly those giving enantioenriched vicinal stereocenters, the reaction of more complex substrates remains underexplored.
Article
Chemistry, Organic
Yixiao Zhang, Pengwei Xu, Qiongli Zhao, Jun Wang, Zhongxing Huang
Summary: Substituted malonic esters are valuable substrates for desymmetrization to tertiary and quaternary stereocenters. A new variation of the desymmetrization has been developed for monosubstituted malonic esters using a pipecolinol-derived tetradentate ligand. This method allows for the preparation of structurally diverse tertiary stereocenters with good yields and enantioselectivity. The enantioenriched products have been demonstrated to have synthetic utility in a mild amination procedure to synthesize chiral amino alcohols.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Wei-Feng Zheng, Jingdan Chen, Xiaotian Qi, Zhongxing Huang
Summary: Stereoselective protonation is a challenge in asymmetric catalysis, but it can convert abundant acid feedstocks into structurally diverse chiral molecules. Researchers have demonstrated an anchoring group strategy to create additional catalyst-substrate interactions, allowing enantioselective decarboxylative protonation to produce alpha-amino acids. This malonate-based synthesis introduces side chains and enables the access of structurally and functionally diverse amino acids.
