Article
Chemistry, Multidisciplinary
Chen-Qiang Deng, Jiao Liu, Jia-Hao Luo, Li-Jin Gan, Jin Deng, Yao Fu
Summary: A robust and highly active homogeneous chiral nickel-phosphine complex has been discovered for the asymmetric hydrogenation of aliphatic gamma- and delta-ketoacids. The mechanism studies revealed the activation of the substrate and stereoselectivity control through hydrogen bonds. Furthermore, this catalytic system can convert biomass feedstock into chiral products without loss of enantioselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Sergio Cuesta-Galisteo, Johannes Schorgenhumer, Xiaofeng Wei, Estibaliz Merino, Cristina Nevado
Summary: This study presents a nickel-catalyzed asymmetric reductive hydroarylation method for synthesizing enantioenriched alpha-arylbenzamides. By using a BIm ligand, diethoxymethylsilane, and aryl halides, aryl groups can be selectively introduced to the internal position of the olefin, creating a new stereogenic center alpha to the N atom with neutral reagents and mild reaction conditions. This provides a straightforward route to pharmacologically relevant motifs found in anticancer drugs, SARS-CoV PLpro inhibitors, and KCNQ channel openers.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Xin Liu, Thomas Werner
Summary: A manganese pincer complex is reported as a versatile catalyst for the transfer hydrogenation of amides, carbamates, urea derivatives, and polyurethanes, leading to the corresponding alcohols, amines, and methanol. This method represents an approach to the indirect reduction of CO2 and shows the first examples of reduction of carbamates and urea derivatives as well as C-N bond cleavage in amides by transfer hydrogenation. The general applicability of this methodology is demonstrated by successful reduction of various compounds with good to excellent yields.
Article
Chemistry, Organic
Pierre Plouard, Ulysse Elmerich, Mina Hariri, Severine Loiseau, Ludovic Clarion, Jean Luc Pirat, Pierre-Georges Echeverria, Tahar Ayad, David Virieux
Summary: Asymmetric transfer hydrogenation (ATH) is a powerful method for synthesizing chiral compounds, but the reduction of alpha-ketophosphonates has been less explored. This study reports an efficient Ru-catalyzed ATH method for a broad range of alpha-ketophosphonates, offering mild conditions, operational simplicity, limited waste generation, broad substrate scope, good to excellent yields, and excellent levels of stereoinduction.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Giuseppe Zuccarello, Suzanne M. Batiste, Hyungdo Cho, Gregory C. Fu
Summary: Due to increasing interest in the pharmaceutical industry, the synthesis of chiral alpha-aminoboronic derivatives has become an important challenge. In this study, we demonstrate the enantioselective synthesis of these derivatives using a chiral copper catalyst generated from commercially available components. Mechanistic studies were also conducted to optimize the process and provide insights into the reaction mechanism.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Hanlin Wei, Hao Chen, Jianzhong Chen, Ilya D. D. Gridnev, Wanbin Zhang
Summary: In this study, an efficient earth-abundant transition-metal nickel catalyzed asymmetric hydrogenation of chiral ethylphosphine products was reported. The products were obtained with up to 99% yield, 96% ee (enantiomeric excess) (99% ee, after recrystallization) and 1000 S/C (substrate/catalyst) ratio. This is also the first study on the asymmetric hydrogenation of terminal olefins using a nickel catalyst under a hydrogen atmosphere. Deuterium-labelling experiments and calculations revealed that the two added hydrogen atoms in the products came from hydrogen gas. Additionally, it was suggested that the reaction involves a Ni-II rather than Ni-0 cyclic process based on the weak attractive interactions between the Ni catalyst and terminal olefin substrate.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Liyao Zeng, Menglong Zhao, Bijin Lin, Jingyuan Song, James H. R. Tucker, Jialin Wen, Xumu Zhang
Summary: A new cobalt catalytic system for asymmetric hydrogenation of ketones was developed using ferrocene-based secondary phosphine oxide ligands. The coordination pattern of cobalt with the ligands was confirmed by X-ray diffraction. The cobalt complexes exhibited high reactivities (up to 99% yield) and good to excellent enantioselectivities (up to 92% ee) in the hydrogenation of ortho-substituted diaryl ketones. Moreover, the diferrocenyl cobalt complex showed intriguing UV-vis absorption and electrochemical properties.
Article
Chemistry, Organic
Yutong Liu, Shuangqiao Li, Xueqin Chen, Hezhong Jiang
Summary: We present a radical-based and photocatalyst-free method that efficiently achieves C(sp(2))-C(sp(3)) cross-coupling reaction for the synthesis of α-aryl ester derivatives. This process involves the reaction between a β-keto ester and an electron-deficient halogenated aryl halide under alkaline conditions, forming an electron donor-acceptor complex that is driven by visible light. From a synthetic standpoint, this newly developed method offers a straightforward approach to obtain arylpropionic acids from readily available and inexpensive starting materials.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Review
Chemistry, Multidisciplinary
Philipp Spiess, Saad Shaaban, Daniel Kaiser, Nuno Maulide
Summary: Umpolung is a term describing the reversal of innate polarity, which has become an important tool in synthetic organic chemistry. In this Account, the authors provide an overview of established methods and summarize their findings in the rapidly developing field of umpolung of carbonyl derivatives. They focus on the alpha-umpolung of amides enabled by electrophilic activation and the enolonium chemistry of ketones enabled by hypervalent iodine reagents. The authors discuss the challenges and achievements of these reactions, as well as mechanistic aspects. Rating: 8/10.
ACCOUNTS OF CHEMICAL RESEARCH
(2023)
Article
Chemistry, Applied
Nithin Pootheri, Sunwoo Lee
Summary: A method for preparing 18O-labeled esters through a Ni-catalyzed three-component reaction has been developed. This method exhibits excellent selectivity and compatibility with various amides and alkyl halides, enabling the synthesis of diverse isotopically labeled esters.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Feng Wan, Nan Wang, Yuxin Zhu, Chuyan Tang, Jerome Claverie, Wenjun Tang
Summary: An efficient asymmetric hydrogenation using a Rh-ArcPhos catalyst has been achieved, resulting in the synthesis of compounds with two chiral centers.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Quang H. Luu, Junqi Li
Summary: This study presents a new reaction strategy for carbon-to-oxygen substitution in the core framework of complex molecules, enabling single atom changes. The oxygen atom insertion is achieved through methylene and Baeyer-Villiger oxidations, followed by a nickel-catalyzed decarbonylation to remove the carbon atom. This reaction sequence was successfully applied to various lactones, and also demonstrated on a natural product and a pharmaceutical precursor.
Article
Chemistry, Multidisciplinary
Zhi-Peng Bao, Xiao-Feng Wu
Summary: This article develops an efficient and convenient palladium-catalyzed carbonylation reaction for the synthesis of 2-cyano-N-acetamide and 2-cyanoacetate compounds. The reaction proceeds under mild conditions via a radical intermediate, suitable for late-stage functionalization. Gram-scale experiment was successfully performed with low catalyst loading, yielding the target product excellently. Additionally, this transformation can be carried out under atmospheric pressure and provides alternative routes to drug precursors.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Liu Shi, Qiang Xiong, Shu-Yi Wu, Yang Li, Peng Shen, Ji Lu, Guang-Yao Ran
Summary: Novel cyclic vinylogous anhydrides were designed and utilized as five-carbon carbonyl synthons for [5 + 5] annulation with vinylethylene carbonates under chiral palladium catalysis. The strategy exhibited excellent regioselectivity, mild conditions, and broad substrate scope, leading to the synthesis of spiro ten-membered lactones bearing oxindole and pyrrolidinone motif in high yield (up to 99%) with moderate to high enantioselectivity (up to 89% ee).
Article
Chemistry, Multidisciplinary
Jiabin Ni, Xiaowen Xia, Danyu Gu, Zhaobin Wang
Summary: In this study, a Ti-catalyzed modular ketone synthesis from carboxylic derivatives and easily accessed gem-dihaloalkanes is described. Notably, this protocol enables the direct catalytic olefination of carboxylic acids. The method features a sequence of olefination and electrophilic transformation, exhibits good functional group compatibility, and allows rapid access to various functionalized ketones. Preliminary mechanistic studies support the intermediacy of plausible alkylidene titanocene and gem-bimetallic complexes.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Inorganic & Nuclear
Deqiang Wang, Guohua Hou, Guofu Zi, Marc D. Walter
Summary: This study describes the synthesis, structure, and reactivity of a new uranium-containing compound with high reactivity towards small organic molecules. Tests have shown that it undergoes various types of reactions when exposed to different organic molecules.
Article
Chemistry, Organic
Guiying Xiao, Shuang Xu, Chaochao Xie, Guofu Zi, Weiping Ye, Zhangtao Zhou, Guohua Hou, Zhanbin Zhang
Summary: An enantioselective hydrogenation method catalyzed by Rh/f-spiroPhos complex has been developed for the synthesis of chiral hydantoins and 2,5-ketopiperazine derivatives with high enantioselectivities up to 99.9% ee under mild conditions.
Article
Chemistry, Inorganic & Nuclear
Shichun Wang, Tongyu Li, Yi Heng, Guohua Hou, Guofu Zi, Marc D. Walter
Summary: Compound 4 reacts with various compounds to yield different metalloorganics and heterocycles, whose structures and properties are studied and explored.
Article
Chemistry, Inorganic & Nuclear
Shichun Wang, Tongyu Li, Yi Heng, Dongwei Wang, Guohua Hou, Guofu Zi, Marc D. Walter
Summary: The uranium bipyridyl metallocene has been studied for its applications in small-molecule activation and C-C coupling reactions.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Suna Han, Xin Shen, Xiaoxue Wu, Chaochao Xie, Guofu Zi, Guohua Hou
Summary: In this study, a Cu-catalyzed highly diastereo- and enantioselective methylboration reaction of diverse heterocyclic compounds was realized for the first time. The reaction provides the corresponding organoboron compounds bearing two adjacent chiral centers with excellent diastereoselectivities and enantioselectivities. This method offers an efficient and highly enantioselective approach for the synthesis of chiral organoboron compounds and their derivatives containing heterocyclic structures.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Siwei Wang, Chaochao Xie, Yu Zhu, Guofu Zi, Zhanbin Zhang, Guohua Hou
Summary: An efficient Ni-(S,S)-Ph-BPE complex has been developed for the asymmetric hydrogenation of cyclic N-acyl hydrazones, leading to the formation of various chiral cyclic hydrazines with high yields and enantioselectivities of over 99%. The hydrogenation reaction can proceed smoothly on a gram scale with low catalyst loading (S/C = 3000) without a decrease in enantioselectivity, and it can be applied to the asymmetric synthesis of a RIP-1 kinase inhibitor.
Article
Chemistry, Multidisciplinary
Tongyu Li, Dongwei Wang, Yi Heng, Guohua Hou, Guofu Zi, Wanjian Ding, Marc D. D. Walter
Summary: Terminal uranium oxido, sulfido, and selenido metallocenes were synthesized and their reactivity was studied. A cycloaddition-elimination methodology was used to prepare the metallocenes employing a useful precursor. The metallocenes showed different reactivities towards alkynes and isothiocyanates, and the results were supported by DFT computations.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Xiaoxue Wu, Yanhao Su, Guofu Zi, Weiping Ye, Guohua Hou
Summary: The asymmetric hydrogenation of a-substituted alkenyl sulfones using Rh-(R,R)-f-spiroPhos complex catalyst has been successfully achieved, resulting in high yields (96-99%) of chiral ?-keto sulfones and simple a-alkyl-substituted sulfones with excellent chemo-/enantioselectivities (86-96% ee) and high turnover numbers (TONs) of up to 4000. This method provides an efficient and high-enantioselectivity strategy for the synthesis of chiral ?-keto sulfones and simple a-substituted sulfones under mild conditions. Additionally, the obtained hydrogenation product can be transformed into other important chiral a-substituted sulfones.
Article
Chemistry, Multidisciplinary
Chaochao Xie, Guiying Xiao, Qianling Guo, Xiaoxue Wu, Guofu Zi, Wanjian Ding, Guohua Hou
Summary: A highly enantioselective rhodium-catalyzed reductive dearomatization of 7-substituted pyrazolo[1,5-a]pyrimidines has been achieved for the first time, yielding chiral 4,5,6,7-tetrahydropyrazolo[1,5-a]pyrimidines with excellent enantioselectivities up to 98% ee. This method also offers an efficient approach for the synthesis of the potent BTK inhibitor, zanubrutinib.
Article
Chemistry, Organic
Chaochao Xie, Qianling Guo, Zhihong Yang, Guofu Zi, Yuping Huang, Guohua Hou
Summary: The Rh/f-spiroPhos complex has been developed for the enantioselective hydrogenation of α-trifluoromethylidene lactams, providing an efficient method for synthesizing various chiral 2,2,2-trifluoroethyl lactams with excellent enantioselectivities (up to 99.9% ee) and high turnover numbers (up to 10,500 TON). Furthermore, the resulting hydrogenation products can be successfully transformed into chiral 2,2,2-trifluoroethyl pyrrolidine, 2-piperidone, and an inhibitor of the donor receptor tyrosine kinase effector Raf.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Inorganic & Nuclear
Tongyu Li, Dongwei Wang, Yi Heng, Guohua Hou, Guofu Zi, Marc D. Walter
Summary: This paper investigates the reaction chemistry of a tetravalent uranium imido complex with a wide variety of substrates.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Shichun Wang, Yi Heng, Tongyu Li, Guohua Hou, Guofu Zi, Marc D. Walter
Summary: This paper discusses the synthesis and reactivity of a phosphinidene compound, as well as its reactions with various molecules. Additionally, the reactivity of the uranium phosphinidene metallocenes in the presence of a Lewis base is evaluated.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Inorganic & Nuclear
Deqiang Wang, Shichun Wang, Tongyu Li, Yi Heng, Guohua Hou, Guofu Zi, Marc D. Walter
Summary: A novel terminal uranium phosphinidene metallocene complex was isolated and its reactivity towards various heterounsaturated molecules was investigated, leading to the formation of carbodithioates, sulfidos, oxidos, metallaheterocycles, and imido complexes in good yields. Additionally, a pseudophosphinimido uranium(III) complex was obtained in good yield by reacting with a diazoalkane derivative. This study provides new insights into the synthesis and applications of organouranium complexes.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Inorganic & Nuclear
Deqiang Wang, Guohua Hou, Guofu Zi, Marc D. Walter
