Article
Chemistry, Multidisciplinary
Mingyue Wu, Zhaobin Han, Huanzhen Ni, Nengzhong Wang, Kuiling Ding, Yixin Lu
Summary: Highly enantioselective and chemodivergent domino reactions have been developed between gamma-substituted allenoates and activated alkenes. Different types of chiral products, with biological relevance and synthetic importance, can be obtained by controlling the structural differences of the substrates under virtually identical reaction conditions.
Article
Chemistry, Multidisciplinary
Zhi-Kai Zhang, Ya-Li Feng, Zheng Ruan, Yuan-Qing Xu, Zhong-Yan Cao, Meng-Hua Li, Chao Wang
Summary: This article presents a practical method for 1,2-diborylation of non-activated monosubstituted alkenes via nickel catalysis. The method shows high tolerance towards functional groups and can be applied for the synthesis of drugs and modification of natural product derivatives. Preliminary mechanistic studies suggest the involvement of a Ni(ii) catalytic cycle.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Basavaraja Durugappa, C. S. Athira, Siddalingeshwar V. Doddamani, Sasidhar B. Somappa
Summary: A facile and efficient method for the synthesis of highly functionalized spiro-oxetane oxindoles has been presented. The reaction, catalyzed by 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), proceeds through a spiro-annulation process between isatins and allenoates. This method is compatible with various isatins containing electron-donating groups (EDGs) and electron-withdrawing groups (EWGs) and provides diverse structures of highly functionalized spiro-oxetane oxindoles relevant to pharmaceuticals.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Dongqiu Li, Fang Cheng, Yuhai Tang, Jing Li, Yang Li, Jiao Jiao, Silong Xu
Summary: The method described involves a phosphine-catalyzed internal redox [4 + 2] annulation of 1,4-enynoates with electron-deficient alkenes, resulting in the efficient synthesis of highly functionalized cyclohexenes with exclusive regioselectivity and high diastereoselectivity under mild conditions.
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
Jiaming Zhang, Jing Luo, Xue Li, Qiaoyu Zhang, Zhoujie Wu, Yu Lan, Donghui Wei
Summary: A computational study was conducted to investigate the mechanisms of beta-isocinchonine-catalyzed asymmetric C(sp(2))-H allylation of trisubstituted allenoates using Morita-Baylis-Hillman (MBH) carbonates for the synthesis of axially chiral tetrasubstituted allenoates. The results suggest that the most energetically favorable pathway involves several steps, including nucleophilic attack, dissociation of BocO(-), C-C bond formation, and catalyst regeneration. The study also highlights the importance of C-H···O and C-H···π interactions in controlling axial and central chirality.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Alexander W. Schuppe, James Levi Knippel, Gustavo M. Borrajo-Calleja, Stephen L. Buchwald
Summary: The study presents a dual CuH- and Pd-catalyzed asymmetric Markovnikov hydroalkenylation method for the synthesis of diverse alpha-chiral olefins, including tri- and tetrasubstituted olefin products. This protocol provides a valuable strategy for rapid generation of structural diversity in complex target syntheses.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Shabbir Ahmed Khan, A. Sanjeeva Kumar, K. C. Kumara Swamy
Summary: DBU-catalyzed spiro-annulation and ring expansion/dominoreaction of delta-acetoxy allenoates with cycl-2-ene-N-sulfonyl hydrazides led to ring-expanded products. On the other hand, cycl-3-ene/ane-N-sulfonyl hydrazones under similar conditions gave pyrazolecores. The key intermediates of spirocyclic and dienyl-amine were isolated and characterized. An extension to (R)-(-)-carvone-derived sulfonyl hydrazide also resulted in ring expansion and formation of pyrazoloazepine.
Article
Chemistry, Multidisciplinary
Panxia Zhao, Jie Chen, Nana Ma, Jingfei Chen, Xiangquan Qin, Chuanfei Liu, Fuquan Yao, Lishan Yao, Longyi Jin, Zhiqi Cong
Summary: The study demonstrates the efficient H2O2-dependent (R)-enantioselective epoxidation of unfunctionalized styrene and its derivatives by site-mutated variants of a unique non-natural P450BM3 peroxygenase in combination with a dual-functional small molecule. The synergistic use of protein engineering and an exogenous DFSM represents an effective strategy to control the enantioselectivity of styrene epoxidation, significantly expanding the chemical scope of P450 enzymes as useful bio-oxidative catalysts.
Article
Chemistry, Organic
Yue Lu, Fangfang Zhu, Xinyu Liu, De Wang
Summary: A novel phosphine-catalyzed asymmetric aza-Morita-Baylis-Hillman reaction has been developed for the synthesis of compounds with tetra-substituted chiral centers. The reaction exhibited high yields and enantioselectivities, and a wide range of substrates could be used. Catalyst switching strategy allowed for the synthesis of diverse enantiomeric products.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Xixia Tang, Lu Qian, Guixia Liu, Zheng Huang
Summary: Asymmetric transfer hydrogenation of 1-aryl-1-alkylethenes with ethanol using a chiral (PCN)Ir complex as the precatalyst has been developed, demonstrating high enantioselectivities, good functional group tolerance, and operational simplicity. This method is also applied to formal intramolecular asymmetric transfer hydrogenation of alkenols without an external H-donor, allowing for the production of a tertiary stereocenter and remote ketone group simultaneously. The utility of the catalytic system is highlighted by gram scale synthesis and the synthesis of the key precursor of (R)-xanthorrhizol.
Review
Chemistry, Multidisciplinary
Senjie Ma, John F. Hartwig
Summary: Catalytic intermolecular hydroamination of alkenes is a valuable method for the synthesis of amines with important applications in various fields. However, achieving high yield and selectivity is challenging due to the lack of thermodynamic driving force and the occurrence of side reactions. Late transition-metal complexes have shown advantages in catalyzing hydroaminations. This Account describes the progress in catalytic hydroamination reactions catalyzed by late transition-metal complexes, including additions to activated and unactivated alkenes, and the development of enantioselective hydroaminations.
ACCOUNTS OF CHEMICAL RESEARCH
(2023)
Article
Chemistry, Multidisciplinary
Peng Lu, Xiang Ren, Haofeng Xu, Dongpo Lu, Yufeng Sun, Zhan Lu
Summary: This study presents an iron-catalyzed highly enantioselective hydrogenation method for the synthesis of chiral alkanes from minimally functionalized 1,1-disubstituted alkenes. A novel chiral 8-oxazoline iminoquinoline ligand and its iron complex have been designed and synthesized to facilitate this transformation. The reaction is operationally simple, utilizing 1 atm of hydrogen gas, and demonstrates good functional group tolerance.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Cole C. Meyer, Zachary J. Dubey, Michael J. Krische
Summary: This study systematically investigates the enantioselective additions to symmetric ketones for the first time. By generating the cyclometallated iridium-PhanePhos complexes in situ, the 2-propanol-mediated reductive couplings were catalyzed, resulting in the formation of branched homoallylic oxetanols and azetidinols.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Wo Nie, Shichao Shen, Cheng Ma
Summary: A rhodium-catalyzed dehydrogenative cycloisomerization of dienylcyclopropane compounds is reported, providing a straightforward approach to highly substituted toluene derivatives in yields of 67-85%. The dienylcyclopropaneimides are produced through a single-step olefination procedure. Preliminary mechanistic studies suggest that an electron-withdrawing group as R is crucial for completing this transformation.
Article
Chemistry, Multidisciplinary
Kaiye Wang, Yanan Xiang, Wei Pan, Hongyu Wang, Na Li, Bo Tang
Summary: In this study, an endoplasmic reticulum-targeted organic photothermal agent was developed to enhance the efficacy of photothermal therapy for tumors. The photothermal agent exhibited excellent targeting ability and biocompatibility, and effectively eradicated tumor cells using near-infrared laser.
CHINESE CHEMICAL LETTERS
(2022)
Article
Chemistry, Organic
Jinsong Hou, Gaosheng Yang, Zhuo Chai
Summary: A novel reaction pathway involving tandem insertion of aliphatic nitriles and unactivated alkenes to the N-H bond of secondary aliphatic amines catalyzed by simple trialkyl rare-earth metal complexes was discovered. This reaction provides an atom-economic and stereoselective approach to a variety of cyclic amidines under mild reaction conditions.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Hongyu Wang, Chen-Fei Liu, Robert T. Martin, Osvaldo Gutierrez, Ming Joo Koh
Summary: This study presents a new directing-group-free, nickel-catalysed strategy for the catalytic addition of carbogenic groups to unactivated and activated olefins with control of regioselectivity, achieving up to 93% yield and >98% site selectivity. The method can be extended to other types of reactions by switching reagents, and mechanistic and computational investigations provide insights into the regiochemical outcome of the reaction. The utility of the method is demonstrated through the concise syntheses of biologically active molecules, and the reported catalyst control principles are expected to advance efforts towards developing general site-selective alkene functionalizations.
Article
Chemistry, Physical
Hongyu Wang, Chen-Fei Liu, Tong-De Tan, Kyna Ru Bin Khoo, Ming Joo Koh
Summary: The study demonstrates a new method for the highly efficient and site-selective 1,2-diarylation of aliphatic-1,3-dienes using N-heterocyclic carbene (NHC)-Ni(0) catalyst, allowing for the synthesis of products containing tertiary or quaternary centers.
Review
Chemistry, Organic
Pei-Jun Yang, Zhuo Chai
Summary: This review outlines the advances achieved in the catalytic asymmetric desymmetrization of meso-aziridines and highlights some promising avenues for further work in this realm.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Qingbing Yuan, Zeming Huang, Zhuo Chai, Dongjing Hong, Shan Zhu, Shuangliu Zhou, Xiancui Zhu, Yun Wei, Shaowu Wang
Summary: We have successfully synthesized and characterized a binuclear copper(I) complex supported by the indolyl-based ligand, and used it as a catalyst to develop a method for delivering various trifluoromethylated azole derivatives. The method exhibits exclusive chemo- and regioselectivity, a broad scope of substrates including alkenes and oxazoles, thiazoles, and good tolerance of functional groups under mild conditions.
Article
Chemistry, Organic
Yaomei Liu, Rui Chen, Lishuai Lu, Dengyu Yin, Fangpei Yan, Xiao-Xuan Li, Hua Xiao, Shilu Fan, Yi-Si Feng
Summary: An efficient copper-catalyzed cross-coupling method was developed for C-(sp(3))-CHF bond formation using allyl phosphate and 2-fluoro-2-(trimethylsilyl) acetate. Under moderate conditions, the reaction showed high conversion and provided a series of monofluoro-alkylation products in good yields, highlighting its practicality for gram-scale reactions.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Dongcheng Zheng, Rui Zhang, Wenlong Chen, Pengfei Yang, Zhuo Chai, Gaosheng Yang
Summary: Under the influence of simple Lewis acid catalysts, 2-(1-aroylcyclopropyl)malonates display unique reactivity in annulation reactions with aryl/alkyl aldehydes, paraformaldehyde, and 1,3,5-triazinanes. Three structurally diverse cyclic products, which are difficult to obtain otherwise, are generated in moderate to good yields with excellent diastereoselectivities. Possible reaction pathways leading to these products are proposed based on control experiment results.
Article
Chemistry, Organic
Fangpei Yan, Rui Chen, Dengyu Yin, Lishuai Lu, Yaomei Liu, Shilu Fan, Hua Xiao, Yanwu Zhu
Summary: A facile and direct approach for chromium-catalyzed terminal alkynes arylation and hydroarylation was developed, providing a useful route for the synthesis of diaryl unsaturated compounds from readily available starting materials in moderate yields.
Article
Chemistry, Organic
Wei Zhou, Zhi-Wen Luo, Hua Xiao, Jun Yi, Jian-Jun Dai
Summary: In this study, a photo-induced radical reaction was developed to convert vinylboronic esters into alkylboronic esters using CuCl2 as a catalyst. The method features mild reaction conditions, easily accessible reagents, and scalability for gram-scale synthesis.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Le Zhang, Ye Liu, Chao-Xu Li, Lei Zhu, Guo-Yin Xiong, Shi-Lu Fan, Jian-Jun Dai, Hua Xiao
Summary: A phosphine-promoted tandem Diels-Alder reaction using pentadienyl 4-nitrobenzoate as a diene precursor with 3-olefinic oxindoles or CF3-activated ketones as dienophiles has been developed. This method provides a metal-free and step-efficient approach for synthesizing exomethylene-bearing spirooxindoles and dihydropyrans, which are privileged structures found in natural products.
Article
Chemistry, Organic
Gaosheng Yang, Dongcheng Zheng, Rui Zhang, Wenlong Chen, Pengfei Yang, Zhuo Chai
Summary: Under the influence of simple Lewis acid catalysts, 2-(1-aroylcyclopropyl)malonates exhibited distinctive reactivities in annulation reactions with aryl/alkyl aldehydes, paraformaldehyde, and 1,3,5-triazinanes. Three structurally diverse cyclic products that are typically difficult to obtain were produced with moderate to good yields and excellent diastereoselectivities. Possible reaction pathways leading to these products were proposed based on control experiments.
Article
Chemistry, Multidisciplinary
Hongyu Wang, Ming Joo Koh
Summary: Generating value-added compounds from abundant feedstock chemicals through simple methods is a longstanding objective in organic synthesis. Regioselective three-component 1,2-dicarbofunctionalization of unactivated alkenes has emerged as a powerful strategy, but inherent challenges have hindered its development. The directing group-free approach represents a promising method for implementing 1,2-dicarbofunctionalization.
CELL REPORTS PHYSICAL SCIENCE
(2022)
Article
Chemistry, Multidisciplinary
Wei Liu, Le Zhang, Ye Liu, Shi-Lu Fan, Jian-Jun Dai, Wei Tao, Hui-Xia Zhu, Hua Xiao
Summary: In this study, a consecutive S(N)2'/S(N)2'' addition of phenol to gamma-vinyl MBH carbonate was performed, leading to the formation of functionalized exocyclohexenes with excellent chemoselectivity. Additionally, using o-hydroxychalcones as pronucleophiles, a series of pharmaceutically intriguing tricyclic chromane derivatives were selectively synthesized through an S(N)2'/S(N)2''/intramolecular Diels-Alder reaction sequence with good diastereoselectivity.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Ling Qi, Pei-Jun Yang, Wen-Tao Ji, Gui-De Tao, Gaosheng Yang, Zhuo Chai
Summary: In this study, we report an efficient strategy for synthesizing compounds with high pharmaceutical value using catalysts. The method is simple and feasible, with mild reaction conditions, and can be used for the synthesis of important drugs.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Faiza Diaba, Gisela Trenchs
Summary: The first violet light-mediated synthesis of gamma- and delta-lactams from N-alkenyl trichloroacetamides is reported in this paper. The reactions are conducted in tetrahydrofuran or 2-methyltetrahydrofuran as the sole solvent without catalysts or additives, under non-anhydrous conditions in an air atmosphere where the solvent serves as the radical initiator.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Feroze Hussain, Sajjad Ahmed, Ashiq Hussain Padder, Qazi Naveed Ahmed
Summary: This study reports a novel and efficient one-pot synthesis method for mixed phosphorotrithioates, which does not require supplementary additives and shows broad applicability.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Hyunjin Oh, Ikyon Kim
Summary: A new 1,2,4-triazole-pyrrolo[1,2-a]pyrazine hybrid system, 6-acylpyrrolo[1,2-a][1,2,4]triazolo[5,1-c]pyrazine, was synthesized using a catalyst-free method. This method involved sequential exposure of pyrrole-2-carbonitrile-derived substrates to DMF-DMA and acyl hydrazide, resulting in the formation of acylated pyrazine and 1,2,4-triazole rings, enabling the installation of various substituents at specific positions on the core skeleton.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Ming Yan, Si-fan Wang, Yong-po Zhang, Jin-zhong Zhao, Zhuo Tang, Guang-xun Li
Summary: Here we developed an efficient photocatalytic approach for the convenient preparation of sulfinamides. The reaction allows for the gram-scale preparation of sulfinamides and the one-pot synthesis of various sulfonyl amides.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Farzaneh Bandehali-Naeini, Zahra Tanbakouchian, Noushin Farajinia-Lehi, Nicolas Mayer, Morteza Shiri, Martin Breugst
Summary: Two tandem catalytic systems were developed for the synthesis of novel 3,4-disubstituted maleimides using the same Ugi adducts. Different maleimide structures can be synthesized using either Pd or Cu catalysis.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Tanya Raghava, Anjan Chattopadhyay, Subhadeep Banerjee, Nivedita Sarkar
Summary: Amine substitution of two ortho fluorine atoms of tetrafluoroterephthalonitrile through SNAr chemistry is easily achievable. But further fluorine substitution is only possible under forcing conditions, yielding valuable fluorophores for bioimaging.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Review
Chemistry, Organic
Anju Chadha, Santosh Kumar Padhi, Selvaraj Stella, Sowmyalakshmi Venkataraman, Thangavelu Saravanan
Summary: Alcohol dehydrogenases are enzymes that use cofactors for oxidation or reduction reactions of alcohols or carbonyl compounds. They are utilized in green chemistry and have applications in the production of pharmaceuticals. Recombinant enzymes have solved the challenge of producing purified enzymes in large quantities. Engineered alcohol dehydrogenases have been used in asymmetric synthesis in industry. Various methods have been established for regenerating expensive cofactors to make the enzymatic process more efficient and economically viable.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
