Article
Chemistry, Organic
Jianzhong Lu, Mengzhen Zhang, Xinxin Zheng, Pei Shen, Yuemeng Xu, Qian Zhang, Yixin Tang, Guozhu Zhang, Rui Guo
Summary: A highly enantioselective ring-opening and isomerization reaction of cyclobutanols catalyzed by rhodium(I) has been developed. This reaction provides a mild, atom-economical, and redox-neutral approach for the synthesis of chiral acyclic ketones with a β-tertiary stereocenter. Cyclobutanols with alkoxy substituents at the C3 position can achieve excellent enantioselectivities and high yields. Mechanistic studies reveal that cyclobutanol only undergoes intramolecular hydrogen migration, and the formation of a (Z)-unsaturated ketone intermediate is crucial for achieving high enantioselectivity.
Article
Chemistry, Multidisciplinary
Shun-Zhong Tan, Peng Chen, Lei Zhu, Meng-Qi Gan, Qin Ouyang, Wei Du, Ying-Chun Chen
Summary: This study demonstrates the application limitation of carboxylic acids as carbon-based nucleophiles, and proposes a method using free (E,E)-2,4-dienoic acids to form complexes with Pd(0) and undergo selective addition reactions with imines to produce dienylated products.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Editorial Material
Multidisciplinary Sciences
Qingli Qian, Buxing Han
Summary: This perspective discusses the progress, future opportunities, and challenges in the CO2 hydrogenation to multicarbon (C2+) products, highlighting some typical related works.
NATIONAL SCIENCE REVIEW
(2023)
Article
Chemistry, Physical
Lu Ouyang, Rui Miao, Zhanhui Yang, Renshi Luo
Summary: Our Ir-catalyzed reductive amination of carboxylic acids with amines allows for the production of structurally diverse N-alkylated amines in good to excellent yields (up to 60 examples). This method offers mild conditions, convenient operations, and excellent functional group tolerance. The synthesis of Cinacalcet and (R)-Fendiline highlights the synthetic value of this protocol.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Hirotsugu Suzuki, Kenji Yoneoka, Sora Kondo, Takanori Matsuda
Summary: The first enantioselective reductive aldol reaction of unprotected alpha,beta-unsaturated carboxylic acids has been developed using a copper/bisphosphine catalyst. This reaction involves the in situ protection and activation of the carboxylic acid using a hydrosilane. The copper enolate formed in situ reacts with an alkyl aryl ketone to produce beta-hydroxy carboxylic acid with excellent enantioselectivity (up to 99% ee). The gram-scale reaction with low catalyst loading and the derivatization of the beta-hydroxy carboxylic acids highlight the practicality of this transformation.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Physical
Yaxin Sun, Chao Wang, Peng Yang, Jie-Yu Yue, Chang Xu, Jianrong Steve Zhou, Bo Tang
Summary: A chiral nickel complex was developed for catalyzing asymmetric transfer hydrogenation of alpha-substituted acrylic acids under mild conditions without high-pressure hydrogen gas. The method allows for the synthesis of chiral compounds, including beta-amino acids and alpha-methyl carboxylic acids, which are useful for the preparation of nonsteroidal anti-inflammatory drugs.
Article
Multidisciplinary Sciences
Vishwas G. Chandrashekhar, Wolfgang Baumann, Matthias Beller, Rajenahally Jagadeesh
Summary: Efficient and general methods for the synthesis of amines using a homogeneous nickel catalyst for hydrogenative cross coupling have been reported. Over 230 functionalized and structurally diverse amines, including pharmaceutically relevant and chiral products, were synthesized using this method.
Article
Chemistry, Multidisciplinary
Aibo Li, Xinjian Song, Qiao Ren, Peiwang Bao, Xinyu Long, Fuli Huang, Lvjiang Yuan, Jianrong Steve Zhou, Xurong Qin
Summary: A cobalt-catalyzed deuteration of amidoacrylates using deuterated methanol resulted in the synthesis of highly enantioselective α,β-dideuterio-α-amino esters with almost complete deuteration (99%). This new protocol was successfully employed for the preparation of dideuterio-α-amino acid fragments in certain drugs, and also applied in the concise synthesis of dideuterio L-DOPA.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Kai Yang, Yukang Wang, Sanzhong Luo, Niankai Fu
Summary: In this study, we developed an electrophotochemical metal-catalyzed protocol for direct asymmetric decarboxylative cyanation of aliphatic carboxylic acids. By utilizing the synergistic merging of electrophotochemical cerium catalysis and asymmetric electrochemical copper catalysis, mild reaction conditions were achieved for the formation and utilization of carbon-centered radicals. This environmentally benign method smoothly converts a diverse array of arylacetic acids into the corresponding alkyl nitriles in good yields and enantioselectivities without using chemical oxidants or pre-functionalization of the acid substrates and can be readily scaled up.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Jing Guan, Jianzhong Chen, Yicong Luo, Lisen Guo, Wanbin Zhang
Summary: A highly selective earth-abundant transition metal copper catalyst was used to achieve the asymmetric hydrogenation of C=O bonds of exocyclic α,β-unsaturated pentanones using H-2. The desired products were obtained with up to 99% yield and 96% enantiomeric excess (99% ee, after recrystallization). The mechanism of hydrogenation was explored through deuterium-labelling experiments and control experiments, revealing that the substrate's keto-enol isomerization rate is faster than that of hydrogenation and the Cu-H complex selectively catalyzes the asymmetric reduction of the carbonyl group. Computational results suggest that the multiple attractive dispersion interactions (MADI effect) between the catalyst with bulky substituents and substrate contribute to stabilizing transition states and reducing by-product formation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Applied
Zhen Yao, Gang Li, Ying Zhou, Lijin Xu, Dong Xue
Summary: The regioselective synthesis of double difluoromethylated allylic products from easily accessible beta,gamma-unsaturated carboxylic acids and difluoromethylation reagents under visible-light photocatalysis is reported. This transformation tolerates various bromodifluoroacetates and fluorinated phosphonates, providing access to various difluoromethylated allylic products in 54-93% yield with 80:20 to 99:1 Z/E, which can not be readily synthesized using the currently known methods. Choosing fac-[Ir(ppy)(3)] as the photocatalyst and 1,4-diazabicyclo[2.2.2]octane (DABCO) as the additive is crucial for the success of this transformation.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Magdalena Tasic, Albert Ruiz-Soriano, Daniel Strand
Summary: This article describes a practical three-step approach to diareno[a,e]cyclooctatetraenes using an efficient copper(I) catalyzed double decarboxylation as the key step. The method relies on cheap and abundant reagents, can be performed on scale, and is also applicable to unsymmetrical derivatives.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Dangui Wang, Wentao Zhang, Xunbo Lu, Hongwei Zhou, Fangrui Zhong
Summary: Novel cinchona alkaloid derived iodide catalysts were developed for the enantioselective oxidative alpha-amination of 2-oxindoles, providing various functionalized spiropyrrolidine oxindoles in high yields and with good enantioselectivities. This iodide/ROOH catalytic system features a one-step synthesis of a catalyst with multiple functionalities, ease of operation, and good scalability, thereby enriching the repertoire of iodide catalysis for enantioselective oxidative coupling reactions.
Article
Chemistry, Applied
Ken Okuno, Bun Chan, Seiji Shirakawa
Summary: Catalytic kinetic resolution is a reliable method for enantioselective synthesis of chiral molecules. However, it is challenging to perform kinetic resolution on racemic compounds with similar substituents at a chiral center. In this study, a kinetic resolution of a-allyl-a-propargyl carboxylic acids was achieved using a chiral bifunctional sulfide catalyst. The utility of the resulting optically active compounds was also demonstrated.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Yiting Gu, Jack R. Norton, Farbod Salahi, Vladislav G. Lisnyak, Zhiyao Zhou, Scott A. Snyder
Summary: Under mild conditions, Cp*Rh(2-(2-pyridyl)phenyl)H catalyzes the selective hydrogenation of the C=C bond in alpha,beta-unsaturated carbonyl compounds, and many isolated double bonds. Mechanistic studies show that no radical intermediates are involved, and the catalyst is homogeneous, providing complementarity to existing protocols for similar hydrogenation processes.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Yu-Hua Deng, Wen-Dao Chu, Xiang-Zhi Zhang, Xu Yan, Ke-Yin Yu, Liang-Liang Yang, Hanmin Huang, Chun-An Fan
JOURNAL OF ORGANIC CHEMISTRY
(2017)
Article
Multidisciplinary Sciences
Mao-Lin Li, Jin-Han Yu, Yi-Hao Li, Shou-Fei Zhu, Qi-Lin Zhou
Article
Chemistry, Multidisciplinary
Liang-Liang Yang, Declan Evans, Bin Xu, Wen-Tao Li, Mao-Lin Li, Shou-Fei Zhu, K. N. Houk, Qi-Lin Zhou
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2020)
Article
Chemistry, Physical
Mao-Lin Li, Yao Li, Jia-Bin Pan, Yi-Hao Li, Song Song, Shou-Fei Zhu, Qi-Lin Zhou
Article
Chemistry, Multidisciplinary
Liang-Liang Yang, Jing Ouyang, Hui-Na Zou, Shou-Fei Zhu, Qi-Lin Zhou
Summary: This study presents a highly enantioselective method for synthesizing chiral propargylsilanes and chiral Allenylsilanes from readily available alkynyl sulfonylhydrazones. The method involves the use of chiral spiro phosphate dirhodium complexes to catalyze asymmetric insertion of alkynyl carbenes into the Si-H bonds of silanes, followed by stereospecific isomerization using a platinum catalyst.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Tian-Yuan Zhao, Ke Li, Liang-Liang Yang, Shou-Fei Zhu, Qi-Lin Zhou
Summary: The highly enantioselective and diastereoselective nickel-catalyzed desymmetrizing cyclization of 1,6-dienes using chiral spiro phosphoramidite ligands provides a new atom- and step-economic approach to chiral spiro lactones and analogues bearing a quaternary stereo-center, which holds significant synthetic application value.
Article
Chemistry, Multidisciplinary
Yu-Tao Zhao, Yu-Xuan Su, Xiao-Yu Li, Liang-Liang Yang, Ming-Yao Huang, Shou-Fei Zhu
Summary: A reliable method for synthesizing chiral gem-diarylmethine boron compounds with high yield, high activity, high enantioselectivity, and broad functional group tolerance has been reported. The borane compounds synthesized by this method can be efficiently transformed into various derivatives with good stereospecificity. Mechanistic studies suggest that the coordination of the borane adduct to the rhodium catalyst interferes with the decomposition of the diazomethane, and that insertion of a rhodium carbene into the B-H bond is likely the rate-determining step.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Liang-Liang Yang, Jin Cao, Tian-Yuan Zhao, Shou-Fei Zhu, Qi-Lin Zhou
Summary: The highly enantioselective Si-H bond insertion reaction of alpha-aryldiazoacetates catalyzed by chiral spiro dirhodium tetraphosphate was successfully developed, leading to the preparation of various chiral alpha-silyl esters with high yield and excellent enantioselectivity. Even challenging substrates for other chiral dirhodium catalysts showed good results in this reaction, making it one of the few successful applications of chiral dirhodium phosphates in asymmetric catalysis.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Mao-Lin Li, Jia-Bin Pan, Qi-Lin Zhou
Summary: This study introduces a strategy for directly preparing chiral alpha-amino acids from ammonia. The cooperative action of copper complexes and chiral hydrogen-bond donors enables enantioselective construction of C-N bonds, achieving high yield and enantioselectivity. The method allows for the production of natural and non-natural chiral alpha-amino acids with various applications.
Article
Chemistry, Physical
Hui-Na Zou, Yu-Tao Zhao, Liang-Liang Yang, Ming-Yao Huang, Jing-Wei Zhang, Meng-Lin Huang, Shou-Fei Zhu
Summary: Chiral propargylic boron compounds have a wide range of potential applications, but the synthesis of these compounds with high enantioselectivity is still unknown. This study reports a catalytic method for the construction of chiral propargylic boron compounds with high enantioselectivity.
Editorial Material
Chemistry, Physical
Liangliang Yang, Jianwei Sun
Summary: An efficient method for enantioselective carbene insertion into ammonia has been discovered, resulting in the production of diverse valuable chiral alpha-amino acids.
Article
Chemistry, Multidisciplinary
Jia-Bin Pan, Zhi-Chun Yang, Xuan-Ge Zhang, Mao-Lin Li, Qi-Lin Zhou
Summary: Here, we present a method for enantioselective phosphoric acid catalyzed amination of ketenes generated from α-aryl-α-diazoketones. Mechanistic studies elucidated the reaction pathway and explained how the catalyst expedited the transformation and controlled the enantioselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Maolin Li, Wesley Harrison, Zhengyi Zhang, Yujie Yuan, Huimin Zhao
Summary: Strategies for achieving remote stereocontrol in asymmetric catalysis with azaarenes have been limited by the inherent rigidity of the azaarene ring structure. However, a photoenzymatic process using an ene-reductase system can modulate the enantioselectivity of remote carbon-centred radicals on azaarenes by chiral hydrogen atom transfer. This allows for the production of a wide range of azaarenes with remote gamma-stereocentres, showcasing the potential of biocatalysts for remote site stereoselectivity.
Article
Chemistry, Multidisciplinary
Li Maolin, Chen Mengqing, Xu Bin, Zhu Shoufei, Zhou Qilin
ACTA CHIMICA SINICA
(2018)