Article
Chemistry, Organic
Changming Xu, Xiangfan Li, Lei Bai
Summary: In this article, a (KOBu)-Bu-t-promoted TBAB-catalyzed alpha-hydroxylation reaction of alpha-methylene aryl esters using O-2 as the oxygen source has been developed. This environmentally friendly and low-cost approach provides a synthesis method for mandelates, which are valuable building blocks widely used in pharmaceuticals.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Nuermaimaiti Yisimayili, Hui Liu, Yun Yao, Chong-Dao Lu
Summary: In this study, alpha-tertiary hydroxyimines were stereoselectively synthesized from enantioenriched N-tert-butanesulfinyl ketimines using potassium tertbutoxide, molecular oxygen, and trimethyl phosphite. The stereoselective hydroxylation of acyclic ketimines with two sterically similar alpha-substituents was achieved by controlling the geometry of the metalloenamine intermediates and the facial selectivity of hydroxylation, demonstrating the synthetic utility through successful diastereoselective synthesis of highly substituted beta-amino alcohols.
Article
Chemistry, Physical
Jae Ho Shim, Seok Hyun Cheun, Hyeon Soo Kim, Deok-Chan Ha
Summary: Michael addition is a significant reaction for synthesizing natural products or complex compounds with biological activities. In this study, a selective Michael addition reaction was achieved by using thiourea as an organic catalyst and double activation mechanism. The reaction exhibited high degree of enantioselectivity and diastereoselectivity, leading to the formation of Michael products with excellent yields.
Article
Chemistry, Multidisciplinary
Philip J. Chevis, Thanika Promchai, Christopher Richardson, Thunwadee Limtharakul, Stephen G. Pyne
Summary: A highly diastereoselective method for the synthesis of syn-beta-amino alcohols and enantioenriched anti-beta-amino alcohols has been developed using different chiral reagents, expanding the application range of existing methods.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Hyoung Min Yeo, Take Hyeon Kim
Summary: The chiral proline amide-isothiouronium salt-based bifunctional organocatalyst, which has more acidic and active N-H bonds compared to thiourea, was prepared by methylating the corresponding chiral thiourea. This catalyst was used for the alpha-hydrazination of aldehydes using azodicarboxylates to produce beta-hydrazino alcohols, beta-amino alcohols, and alpha-amino acid derivatives. Enantioselective alpha-hydrazination of aldehydes was successfully carried out with the amide-isothiouronium salt as a chiral catalyst, resulting in high to quantitative yields and excellent enantioselectivities (up to 99% ee) of various hydrazino aldehydes in the presence of a benzoic acid additive.
Article
Chemistry, Organic
Rui-Zhi Huang, Zhan-Cai Ma, Yuan Huang, Yu Zhao
Summary: A novel cobalt/zinc bimetallic catalysis system was developed for the efficient and enantioselective synthesis of tertiary propargylic alcohols. The system utilized commercially available catalysts and achieved high yields and good enantioselectivities.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Yuki Uwaso, Naoki Yokoyama, Taichi Kano
Summary: Novel axially chiral biphenyl-based amine catalysts were synthesized from dibromopyrenes, and these chiral amines proved to be effective catalysts for asymmetric reactions through enamine intermediates.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Bei Zhou, Yu-Juan He, Yun-Feng Tao, Lan-Xiang Liu, Min Hu, Zu-Hui Chang, Hong Lei, Jun Lin, Tong Lin, Guan-Ben Du
Summary: A novel electrocatalytic process was developed to prepare alpha,alpha-gem-dihalide ketones in an environmentally friendly manner. The reaction exhibited high yields of about 80% under ambient conditions without inert gas protection. The study also discovered a special dimer condensation phenomenon.
Article
Chemistry, Organic
Jin-Rui Li, Yun Yao, Chong-Dao Lu
Summary: A stereocontrolled electrophilic amination approach was employed for the synthesis of α-aminoketone derivatives with less accessible α-tetrasubstituted stereocenters. Stereospecific α-deprotonation of ketimines followed by nucleophilic attack of azodicarboxylic derivatives afforded α-aminated products in high yields with excellent stereoselectivities.
Article
Chemistry, Multidisciplinary
Sijing Wang, Cefei Zhang, Da Li, Yuqiao Zhou, Zhishan Su, Xiaoming Feng, Shunxi Dong
Summary: N-heterocyclic olefins (NHOs) with electron-rich and highly polarized C=C double bond possess strong basicity and high nucleophilicity due to the donating property of nitrogen atoms. In this study, a new type of chiral aminederived C-2-symmetric NHOs was developed and used as efficient chiral bifunctional organocatalysts for asymmetric alpha-functionalization of beta-ketoesters. With as low as 0.1 mol% catalyst loading, the desired amination and trifluoromethylthiolation products were obtained in good yields with high enantioselectivities (up to 99% yield and 99% ee). Experimental studies and theoretical calculation revealed the crucial role of hydrogen-bonding interaction upon protonation and other weak interactions between substrate and catalyst in enantiocontrol.
SCIENCE CHINA-CHEMISTRY
(2023)
Article
Chemistry, Organic
Jiaming Liu, Bo Su, Ming Chen
Summary: A stereoselective synthesis of (E)-delta-vinyl-homoallylic alcohols has been developed using copper-catalyzed allylation of alpha-vinyl allylboronate with aldehydes or ketones, resulting in high E-selectivities. The reaction proceeds via the Curtin-Hammett principle through the intermediacy of alpha-vinyl allylic copper species to provide the alcohol products with high E-selectivities.
Article
Chemistry, Organic
Peng-Wei Xu, Xiao-Yuan Cui, Chen Chen, Feng Zhou, Jin-Sheng Yu, Yu-Fei Ao, Jian Zhou
Summary: This study describes an unprecedented catalytic enantioselective cyanation of ketonitrones using a bifunctional cyanating reagent, Me-2(CH2Cl)SiCN, leading to the synthesis of optically active N-hydroxyl-alpha-amino nitriles. The use of this reagent not only achieves high enantioselectivity but also allows for diversification reactions of the resulting silylated adducts. Additionally, this work highlights the potential of tetrasubstituted C.N bonds for asymmetric synthesis of N-hydroxy alpha-amino acids and other N-hydroxy tertiary amines.
Article
Chemistry, Organic
Yingying Cai, Chi Liu, Guangying Liu, Chengxi Li, Huanfeng Jiang, Chuanle Zhu
Summary: A general and practical method for the synthesis of alpha,alpha-difluoro(arylthio)methyl oxetanes has been reported. This method involves the reaction of alpha,alpha-difluoro(arylthio)methyl ketones with trimethylsulfoxonium halides, and features mild conditions, operational simplicity, a broad substrate scope, and high yields.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Jian Song, Wen-Hua Zheng
Summary: A highly enantioselective kinetic resolution of racemic 1,3-amino alcohols via O-Acylation was achieved using a chiral organotin catalyst. The reaction showed excellent efficiency and high enantioselectivity, with better selectivity for anti-1,3-amino alcohols.
CHEMICAL COMMUNICATIONS
(2022)
Article
Multidisciplinary Sciences
Haichao Liu, Vincent Ho Man Lau, Pan Xu, Tsz Hin Chan, Zhongxing Huang
Summary: The article presents a dinuclear zinc-catalyzed desymmetric approach for the synthesis of chiral alpha-tertiary amines and tertiary alcohols. The method selectively hydrosilylates esters, enabling the synthesis of valuable structures in organic synthesis and drug discovery.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Huixin Luo, Wei Tang, Hongyu Liu, Xiangmei Zeng, William Shu Ching Ngai, Rui Gao, Heyun Li, Ran Li, Huangtao Zheng, Jianting Guo, Fangfei Qin, Gang Wang, Kexin Li, Xinyuan Fan, Peng Zou, Peng R. Chen
Summary: The interactions between RNA and proteins are crucial for cellular processes. This study developed a photocatalytic crosslinking strategy combined with mass spectrometry and RNA sequencing to study the composition and dynamics of protein-RNA interactions. The approach identified numerous RNA binding proteins in human cells and investigated the dynamic changes of RBPs in macrophage cells and their interactions with SARS-CoV-2 RNA.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
William Shu Ching Ngai, Shaojun Yang, Xiangmei Zeng, Yanjun Liu, Feng Lin, Xin Wang, Heng Zhang, Xinyuan Fan, Peng R. Chen
Summary: This article reports a bioorthogonally activatable base editor called BaseBAC, which can initiate pyroptosis in specific cells in situ and on demand. By establishing a bioorthogonal blockage on the PAM-interacting residue to control the enzymatic activity of a cytosine base editor, BaseBAC enables control over pyroptosis.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Ziqi Liu, Xiao Xie, Zongyu Huang, Feng Lin, Shibo Liu, Zujie Chen, Shengnan Qin, Xinyuan Fan, Peng R. Chen
Summary: In this study, we report a extracellular-targeted photocatalytic decaging system for spatially resolved cell tagging and surface proteome profiling. By conjugating an antibody to the photocatalysis system, we achieved targeted photocatalytic decaging on cell surfaces, allowing selective cell tagging in cell mixture and tumor xenografts. Furthermore, we combined quinone methide decaging chemistry with the photocatalytic system to achieve spatially resolved membrane proteome profiling, revealing potential protein clusters. Finally, we expanded our strategy to photocatalytic prodrug decaging for selective tumor cell killing.
Article
Chemistry, Applied
Maria Biosca, Pol de la Cruz-Sanchez, Daniel Tarr, Patricia Llanes, Erik A. Karlsson, Jessica Margalef, Oscar Pamies, Miquel A. Pericas, Montserrat Dieguez
Summary: A chiral phosphine-triazole ligand has been developed for the Ir-catalyzed asymmetric hydrogenation of exocyclic benzofused alkenes, which overcomes previous limitations and exhibits excellent enantioselectivity. The catalyst shows good tolerance towards various substituents and substitution patterns at both aromatic rings, making it an effective tool for hydrogenation of exocyclic olefins.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Leijie Zhou, Nicola Zanda, Moreshwar Chaudhari, Mariane Felicio Da Silva, Miquel A. . Pericas
Summary: A family of polystyrene-supported ligands based on the design of Defieber and Carreira were developed and successfully applied in the iridium-catalyzed asymmetric allylic amination of unmasked allylic alcohols, resulting in 27 examples with up to 99% enantiomeric excess. Two functional resins, L1 and L4, demonstrated significant advantages including easy preparation, ligand recyclability, and convenient handling for sequential use. Notably, the catalytic use of iridium complexes of L1 and L4 allowed for the efficient reuse of expensive iridium metal, which is not achievable under homogeneous conditions with monomeric complexes.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Editorial Material
Chemistry, Multidisciplinary
Xinyuan Fan, Peng R. Chen
SCIENCE CHINA-CHEMISTRY
(2023)
Article
Chemistry, Physical
Manuel R. Rodriguez, Anabel M. Rodriguez, Sara Lopez-Resano, Miquel A. . Pericas, M. Mar Diaz-Requejo, Feliu Maseras, Pedro J. Perez
Summary: In the context of copper-catalyzed nitrene transfer to olefins, this study challenges the general assumption that the X ligand is displaced from the coordination sphere. Through experiments with well-defined copper(I) complexes, it is demonstrated that the catalytic and mechanistic behavior depends on the presence or absence of the chloride ligand bonded to the metal center, with different turnover-limiting steps.
Article
Chemistry, Organic
Nicola Zanda, Ludovica Primitivo, Moreshwar Chaudhari, Arjan W. Kleij, Miquel A. Pericas
Summary: A continuous flow organocatalytic synthesis of formamides has been developed using amines and CO2 reaction partners in the presence of a silane reductant. The process allows the preparation of a broad family of N-substituted formamides in good yield. The heterogenized catalyst and reductant have been optimized to achieve high productivity.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Fuhu Guo, Shiquan Shan, Xu Gong, Cancan Dai, Zhengjun Quan, Xiamin Cheng, Xinyuan Fan
Summary: We propose a novel and effective photocatalytic method for the methylation of & beta;-diketones with controllable degrees of deuterium incorporation by developing new methyl sources. By utilizing a methylamine-water system and a cascade assembly strategy, we synthesized methylated compounds with varying degrees of deuterium incorporation. This work demonstrates the utility of readily available reagents, methylamines and water, as a new methyl source, and provides a simple and efficient strategy for the synthesis of degree-controllable deuterium-labelled compounds.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Arianna Brandolese, David H. Lamparelli, Miquel A. . Pericas, Arjan W. Kleij
Summary: A commercially available Lipase B from Candida antarctica immobilized onto a macroporous support (Novozym 435) was used as a benign oxidant for the epoxidation of various biorenewable terpenes in the presence of H2O2. The epoxidation protocol was explored under both heterogeneous batch and continuous flow conditions. The catalyst showed good recyclability under batch conditions for 10 cycles and could be used for more than 30 hours under continuous flow operation. This sustainable flow epoxidation allows for the production of gram quantities of terpene epoxides and the post-functionalization of biobased polymers.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2023)
Review
Chemistry, Multidisciplinary
Yanjun Liu, Yun Ge, Ruxin Zeng, William Shu, Ching Ngai, Xinyuan Fan, Peng R. Chen
Summary: Enzyme- and catalyst-generated reactive species have been utilized for covalently labeling biomolecules within a short range of a specific location in cells or at the cell-cell interface. These proximity labeling strategies, due to their high spatial resolution, have been combined with various bioanalytical techniques to study dynamic and complex biological processes. This review focuses on the development and applications of enzyme- and catalyst-triggered proximity chemistry for identifying protein interaction networks and cell-cell communications in living systems.
Article
Chemistry, Multidisciplinary
Xianrui Zhang, Haoran Huang, Yuan Liu, Zhigang Wu, Fengzhang Wang, Xinyuan Fan, Peng R. Chen, Jie Wang
Summary: Site-specific protein decaging by light is an effective approach for manipulating protein activities. A genetically encoded photocaged Asp was developed and used for the photocontrolled manipulation of various proteins, including firefly luciferase, kinases, and GTPase. This new tool may have broad applications for studying protein functions and biological processes in living cells.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Xianrui Zhang, Haoran Huang, Yuan Liu, Zhigang Wu, Fengzhang Wang, Xinyuan Fan, Peng R. Chen, Jie Wang
Summary: Site-specific protein decaging by light is an effective approach for manipulating protein activities in a gain-of-function manner. However, decaging strategy has not been extended to aspartic acid (Asp), an essential amino acid residue. We reported a genetically encoded photocaged Asp and demonstrated its application in manipulating various proteins as well as mimicking in situ phosphorylation events on kinases.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Xuan Liang, Shan Qian, Zhizheng Lou, Renming Hu, Yuchen Hou, Peng R. Chen, Xinyuan Fan
Summary: The development of a biocompatible photocatalytic technology termed CAT-NIR enables the spatiotemporal manipulation of biological processes in living animals using external near infrared light (NIR). This system utilizes Os(II) terpyridine complex as an efficient NIR photocatalyst for deboronative hydroxylation reactions, resulting in the release of bioactive molecules. CAT-NIR also allows for the regulation of affibody binding to cell surface receptors through genetic code expansion and computer-aided screening, providing a selective cell tagging technology with external NIR light.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Moreshwar B. Chaudhari, Prachi Gupta, Patricia Llanes, Leijie Zhou, Nicola Zanda, Miquel A. Pericas
Summary: In this study, the merging of polymer-supported asymmetric organocatalysis with continuous flow in a packed bed reactor was successfully used for the synthesis of indoloquinolizidines. A highly enantioselective, solvent-free and rapid conjugate addition reaction in continuous flow allowed the preparation of multigram amounts of relevant oxodiesters. The obtained Michael adducts were then used for the efficient diastereoselective synthesis of indoloquinolizidines through cascade Pictet-Splengler cyclisation-lactamisation in continuous flow. The conversion of enantiopure Michael adducts into delta-lactones via telescoped reduction/cyclisation in continuous flow was also explored.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
