Article
Chemistry, Multidisciplinary
Jian Zhou, Ling Meng, Shujuan Lin, Baohua Cai, Jun (Joelle) Wang
Summary: We report a straightforward Pd-catalyzed ring-opening hydrophosphinylation reaction of methylenecyclopropanes (MCPs) via highly selective C-C bond cleavage. This method allows for rapid and efficient access to a wide range of chiral allylic phosphine oxides in good yields and high enantioselectivities.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Applied
Tao Yi, Quan Liu, Yue Zhang, Jinhao Huang, Zhigang Zeng, Yunfeng Chen
Summary: A copper-catalyzed cascade reaction was reported for the selective oxidative cleavage of C-C bonds in β-alkyl nitroolefins, followed by oxidative amidation with amines or amides. The reaction showed high selectivity and yielded α-ketoamides with 66-88% yields. Mechanistic studies revealed that the reaction occurred on more electron-rich allylic nitro tautomers originating from the equilibrium of conjugated nitroalkenes.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Physical
Jia-nan Teng, Rui Zhu, Xinglong Li, Yao Fu
Summary: In this study, cobalt oxide hydrate supported on metal oxides was prepared as a catalyst for the oxidative cleavage of C(OH)-C bond in alcohols using molecular oxygen as the oxidant, achieving high selectivity in product formation. The catalyst was characterized using various techniques and a reaction mechanism was proposed based on the results. The heterogeneous catalytic system showed good recycling performance without the need for any additives.
Article
Chemistry, Organic
Chuan-Ming Hong, Si-Qi Xiong, Xue Zhang, Kai-Xian Ma, Qing-Hua Li, Tang-Lin Liu
Summary: This paper discloses a silver-catalyzed 1,3-aza-benzyl migration of allyl alcohols by utilizing chelation-assisted selective cleavage of an unstrained C(sp3)-C(sp3) bond. This approach provides an available, efficient, high atom-economic, and environmentally benign procedure, leading to alkylation products with broad substrate scopes and excellent yields. The migration proceeds via a one-pot, two-step process involving a free-state alkyl metal species.
Article
Chemistry, Multidisciplinary
Peipei He, Bo Chen, Liang Huang, Xixi Liu, Jingzhong Qin, Zehui Zhang, Wen Dai
Summary: A novel and efficient protocol for the direct synthesis of amides via heterogeneous manganese-oxide-catalyzed successive cleavage and amidation of C-C bonds in alcohols is reported. This method shows high catalytic activity for a wide range of primary and secondary alcohols, as well as model compounds, resulting in the formation of shorter-chain amides.
Article
Chemistry, Organic
Fusheng Bie, Xuejing Liu, Han Cao, Yijun Shi, Tongliang Zhou, Michal Szostak, Chengwei Liu
Summary: The Pd-catalyzed double-decarbonylative synthesis of aryl thioethers involves an aryl exchange reaction between amides and thioesters, with amides serving as aryl donors and thioesters as sulfide donors. The use of Pd/Xantphos without any additives promotes aryl exchange by C(O)-N/C(O)-S cleavages, allowing for a wide variety of amides and sulfides to be used in the reaction.
Article
Chemistry, Multidisciplinary
Miao Wang, Jinglan Wen, Yahao Huang, Peng Hu
Summary: An efficient method has been developed for selective degradation of styrene-related plastics under gentle conditions through multiple oxidation, catalyzed with inexpensive iron salts under visible light using oxygen as a green oxidant. Furthermore, simple iron salts could be used as additives for degradable plastics.
Article
Chemistry, Organic
Jia-Hui Liu, Xue-Jiao Lv, Yan-Kai Liu
Summary: An asymmetric retro-Claisen reaction of alpha-mono-substituted beta-diketones and quinones (or quinone imine) has been developed using a chiral aza-bisoxazoline-Zn(II) complex as a catalyst. The reaction involves conjugate addition, arylation, hemiketal anion-initiated C-C bond cleavage, and enantioselective protonation of enolate, leading to the formation of functionalized alpha-arylated ketones with a tertiary stereogenic center in high enantioselectivities. Importantly, biologically significant benzofuran and gamma-butyrolactone derivatives can be synthesized using this protocol.
Article
Chemistry, Organic
Weiyou Zhou, Anwei Wang, Zhenji Kong, Xiaoting Tian, Zhenzhen Xia, Zhihui Zhang, Mingyang He, Qun Chen, Shixin Sun
Summary: A convenient catalytic protocol using CuCoFe layered double hydroxide (LDH) for efficiently constructing indoline-fused tetrahydroisoquinolines has been described. The research offers a unique opportunity to develop a synthetic methodology for N-containing polycyclic compounds.
Article
Chemistry, Multidisciplinary
Ziwei Zhao, Zhanrong Zhang, Qinglei Meng, Bingfeng Chen, Jinliang Song, Huizhen Liu, Buxing Han
Summary: Effectively cleaving and functionalizing C(OH)-C bonds is crucial for producing valuable chemicals from renewable biomass resources. The inert nature of C(OH)-C bonds and various side reactions associated with hydroxyl groups hinder their oxidative cleavage efficiency and selectivity. Converting secondary alcohols to aldehydes is particularly challenging due to the tendency of over-oxidation. Noble-metal catalysts are necessary to achieve satisfactory aldehyde yields.
Editorial Material
Chemistry, Multidisciplinary
Rui Zhang, Guangbin Dong
Summary: In this issue of Chem, Morandi and coworkers describe an exciting reversible transfer hydroarylation reaction between ketones and unstrained arylated alcohols. The reaction involves a Rh-catalyzed beta-aryl elimination process, allowing for the transfer of an aryl group from the alcohol to the ketone substrate and providing a milder alternative to conventional Grignard and organolithium addition chemistry.
Article
Chemistry, Multidisciplinary
Jianxiao Li, Dan He, Zidong Lin, Liying Cen, Wanqing Wu, Huanfeng Jiang
Summary: This study describes the first NHC-palladium-catalyzed regioselective oxyarylation of oxime ether in a task-specific ionic liquid via C(sp(3))-O and C(sp(2))-O bond cleavage. The combination of the basic ionic liquid [C(3)NH(2)mim]Br and NHC-Pd catalyst IPr-Pd-Im-Cl-2 plays a crucial role in this transformation. The new approach provides a practical and straightforward route to access a broad range of structurally diverse 4-arylisoxazoles with good yields and excellent regioselectivities.
Article
Chemistry, Multidisciplinary
Guangying Tan, Mowpriya Das, Ivan Maisuls, Cristian A. Strassert, Frank Glorius
Summary: The rhodium-catalyzed dealkenylative arylation of alkenes with arylboronic compounds provides an unconventional access to bi(hetero)aryls with excellent chemoselectivity. This method enables the cleavage of C(aryl)-C(alkenyl) and C(alkenyl)-C(alkenyl) bonds in various alkenes and 1,3-dienes, leading to the efficient construction of novel organic fluorescent molecules with excellent photophysical properties.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Xiao-Di Su, Zhu-Sheng Yang, Wei Gong, Zhi-Xiang Wang, Xiang-Yu Chen
Summary: We have discovered that N-heterocyclic nitreniums (NHNs) can act as efficient catalysts for charge transfer complex without the need for any additives. The NHN cation acts as an electron acceptor, while the counter-ion I- serves as an electron donor, enabling the synthesis of diverse trisubstituted alkenes and heterocycles.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Divya Rohini Yennamaneni, Vasu Amrutham, Krishna Sai Gajula, Murali Boosa, Ramulamma Madasu, Narender Nama
Summary: Researchers successfully synthesized a wide range of quinazolin-4(3H)-ones using a heterogeneous beta zeolite catalyst through selective cleavage of the C-C bond of 1,3-diketones. This method offers a green and feasible approach by avoiding toxic transition metals, additives, and corrosive oxidants.
SUSTAINABLE CHEMISTRY AND PHARMACY
(2022)
Article
Chemistry, Multidisciplinary
Manish Shetty, Huamin Wang, Feng Chen, Nicholas Jaegers, Yue Liu, Donald M. Camaioni, Oliver Y. Gutierrez, Johannes A. Lercher
Summary: The dehydration rates of alkanols catalyzed by hydronium ions are enhanced by the steric confinements of zeolite pores and intraporous intermolecular interactions. Different zeolite structures lead to varying activation enthalpies for alkanol dehydration, affecting the overall reaction rate.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Applied
Guodong Zhang, Yihan Cheng, Matthias Beller, Feng Chen
Summary: The recent research focus on utilizing carbon dioxide for organic synthesis has led to advancements in carboxylations using visible light photoredox and transition-metal dual catalysis, creating new pathways for constructing carboxylates.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Physical
Feng Chen, Manish Shetty, Meng Wang, Hui Shi, Yuanshuai Liu, Donald M. Camaioni, Oliver Y. Gutierrez, Johannes A. Lercher
Summary: The rate of acid-base-catalyzed dehydration of alcohols depends strongly on the solvent and the environment of the acid sites. Brønsted acidic sites in large-pore zeolites catalyze cyclohexanol dehydration at significantly higher rates than hydrated hydronium ions in aqueous phase. The difference in turnover rates between the two solvents is much larger in large-pore zeolites compared to medium-pore zeolites. Additionally, the mechanism of cyclohexanol dehydration varies depending on the zeolite structure, with E1 elimination being dominant except for a monomer dehydration route on H-MFI which follows an E2-type mechanism.
Article
Chemistry, Organic
Pan Gao, Qingzheng Zhang, Feng Chen
Summary: A new protocol for vinyl sulfide synthesis has been developed using an alkoxy base without the need for metal catalysts. This method allows for the conversion of aryl and alkenyl sulfonium triflates with various functionalities into vinyl sulfides with excellent reactivity. The reaction conditions are mild and safe, without the use of catalysts, transition metals, high-pressure gases, or high temperatures, while still maintaining efficiency.
Article
Chemistry, Multidisciplinary
Guodong Zhang, Ye Tian, Chengyu Zhang, Xiang Li, Feng Chen
Summary: Herein, a new decarboxylative Minisci-type reaction of N-heteroarenes with silanecarboxylic acids under photo- or silver-mediated conditions is reported. This C-H silylation strategy provides efficient access to diverse N-heteroarylsilanes in moderate to excellent yields with high regioselectivity, among which Ag-catalysed decarboxylation of silanecarboxylic acids furnishes an unprecedented method for silyl radical generation.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Meiling Zhu, Haitao Tian, Sanxia Chen, Wenxuan Xue, Yanhong Wang, Hongcheng Lu, Ting Li, Feng Chen, Conghui Tang
Summary: Herein, we report a cobalt N,N-bidentate complex catalyzed reductive formylation of N-heteroarenes for the generation of N-formyltetrahydroquinoline (FTHQ) derivatives. Formic acid was used as a transfer hydrogenation reagent, which is safe, abundant, and easy to handle. This work represents the first homogeneous system for the reductive formylation of N-heteroarenes, where the metal ligand cooperated dehydrogenation is crucial for the success of this transformation. Deuteration labeling experiments and Hammett analysis were conducted, suggesting a plausible mechanism.
JOURNAL OF CATALYSIS
(2022)
Article
Chemistry, Physical
Guodong Zhang, Chengyu Zhang, Haijun Jiao, Feng Chen
Summary: The compatibility between photogenerated silyl radicals and transition metal catalysis in synthetic organic chemistry remains a challenge. Herein, we present a protocol for photoredox/nickel catalyzed allylic silylation of allyl acetates using a silyl radical intermediate. This method provides a modular synthesis of substituted allylsilanes from silanecarboxylic acids.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Organic
Guodong Zhang, Lei Wang, Liping Cui, Pan Gao, Feng Chen
Summary: Here, a novel photoredox-catalysed strategy is presented to synthesize gem-difluoroallylarenes from alpha-trifluoromethylalkenes with sterically hindered primary amines via C-N and C-F bond activation. This deaminative and defluorinative allylation exhibits broad compatibility with various functional groups and sterically hindered α-3° and 2° primary amines.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Guodong Zhang, Chengyu Zhang, Ye Tian, Feng Chen
Summary: In this study, a concise and efficient method for the synthesis of diverse nitrile compounds from ubiquitous carboxylic acids was achieved using an inexpensive iron catalyst. The method demonstrated compatibility with primary, secondary, tertiary, and aryl carboxylic acids, as well as various functional groups.
Article
Chemistry, Physical
Pan Gao, Liping Cui, Guodong Zhang, Feng Chen
Summary: A catalytic defluorosilylation method is developed, providing concise and modular synthetic routes for gem-difluoroallylsilanes. Trifluoromethylalkenes and silacarboxylic acids are used as easy-to-prepare and stable silyl radical precursors. This method utilizes photoredox catalysis and features a unique decarboxylation followed by defluorosilylation without extra hydrogen atom transfer catalysis, offering mild reaction conditions and a broad substrate scope applicable to diverse electron-rich and electron-poor groups.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Multidisciplinary
Pan Gao, Qingzheng Zhang, Yicheng Li, Liping Cui, Xinting Fan, Guodong Zhang, Feng Chen
Summary: Radicals can be formed rapidly through direct irradiation of an electron donor-acceptor (EDA) complex. Here, we demonstrate a photocatalyst-free method for synthesizing gem-difluoroalkenes by photo-irradiating EDA complexes, which can be generated in situ between N-alkylpyridinium salts and Hantzsch ester without any additional additives. Various readily available alkylamines undergo deaminative defluoroalkylation to yield the corresponding gem-difluoroalkenes. This reaction system exhibits high reactivity, good tolerance towards different functional groups, and provides a practical and efficient approach to a wide range of alpha-alkyl-substituted gem-difluoroalkenes.
Review
Chemistry, Organic
Xinyin Wu, Pan Gao, Feng Chen
Summary: The utilization of aryl radicals as open-shelled intermediates is important in synthetic chemistry, but current methods for generating aryl radicals are inefficient. Sulfonium salts have emerged as appealing sources for generating aryl radicals due to their unique structure and chemical tendencies. This review focuses on the mechanisms of cleaving C-S bonds in sulfonium salts to generate aryl radicals. The development of synthetic applications using aryl sulfonium salts as precursors is also discussed.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Guodong Zhang, Kaiping Wang, Duo Zhang, Chengyu Zhang, Wei Tan, Zhanzhan Chen, Feng Chen
Summary: This study presents a visible-light-facilitated transition-metal-free allylic silylation reaction, which efficiently synthesizes substituted allylsilanes under mild conditions. The protocol utilizes an inexpensive organophotocatalyst and shows good compatibility with readily available allyl sulfones and stable silanecarboxylic acids. Furthermore, this strategy is also compatible with vinyl sulfones, allowing access to vinylsilanes. The silver catalytic system provides an alternative approach for the decarboxylative allylation of silanecarboxylic acids.
Article
Chemistry, Applied
Feng Chen, Sungmin Kim, Dushyant Barpaga, John. L. L. Fulton, Radha Kishan Motkuri, Oliver. Y. Y. Gutierrez, Donald. M. M. Camaioni, Johannes. A. A. Lercher
Summary: Bronsted-acid sites are introduced on the ZrO2 nodes of UiO-66 MOFs via -OSO3H groups. These sites exhibit strong Bronsted acidity and are active for cyclohexanol and ethanol dehydration reactions in different phases. The activity of Bronsted acid sites at nodes is improved by increasing sulfur concentration, which leads to the formation of two interacting groups [(&mu(3)-OSO3H)(2)] through hydrogen bonding. The catalytic activity can be manipulated by functionalizing zirconia nodes of the MOF framework.
TOPICS IN CATALYSIS
(2023)
Article
Chemistry, Physical
Xugang Yang, Zaihao Yuan, Minghao Zhou, Feng Chen, Bo-Qing Xu, Hui Shi
Summary: A quantitative assessment was conducted on four types of Zr catalysts for the Meerwein-Pondorf-Verley (MPV) reductions, revealing significant differences in the relative fraction of active sites (13-78% of total Zr) and turnover rates (>300-fold) among the catalysts. The results also showed that the hydride shift remained as the sole rate-limiting step, but the free energy barriers and kinetic isotope effects varied significantly among the catalysts, indicating diverse transition state structures and energetics.
