Article
Chemistry, Multidisciplinary
Yan-Dong Zhang, Xiao-Yu Li, Qian-Kun Mo, Wen-Bin Shi, Jia-Bao Zhao, Shou-Fei Zhu
Summary: In this study, we developed new Co complexes with cyclopropane-based diphosphine ligands that can catalyze highly chemo-, regio-, and stereoselective hydroboration reactions of unsymmetrical internal alkynes. These reactions exhibit unusual regioselectivity, leading to the synthesis of trisubstituted alkenylborates and alkenes with different stereochemistry.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Benjamin A. Suslick, T. Don Tilley
Summary: A single-component Co(-I) catalyst has been developed for olefin hydroarylations with (N-aryl)aryl imine substrates under mild reaction conditions, providing good yields. The catalysis occurs in a regioselective manner, resulting in different products for different substrates, and can tolerate certain functional groups.
Article
Chemistry, Multidisciplinary
Yang'en You, Shaozhong Ge
Summary: An enantioselective cobalt-catalyzed hydrosilylation/cyclization reaction of 1,6-enynes with secondary and tertiary hydrosilanes produced chiral organosilane products in high yields and excellent enantioselectivity, which could be further converted into a variety of chiral five-membered heterocyclic compounds without loss of enantiopurity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Philip Andreetta, Robert T. Martin, Charafa Souilah, Angel Renteria-Gomez, Zhihui Song, Yas Khorramshahi Bayat, Sergei Ivlev, Osvaldo Gutierrez, Alicia Casitas
Summary: In this study, a cobalt(I)-catalyzed regioselective allylic alkylation reaction of tertiary allyl carbonates with 1,3-dicarbonyl compounds was developed. A series of tetrahedral cobalt(I) complexes with commercially available bidentate bis(phosphine) ligands were synthesized and investigated as catalysts. The results showed that one specific catalyst exhibited high yields and excellent regioselectivity for the branched product in the alkylation of various tertiary allyl carbonates.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Applied
Jing Tian, Daqian Xu, Wei Sun
Summary: Several cobalt(II) complexes supported by tetradentate and tridentate ligands have been prepared and characterized. X-ray crystallographic analysis shows that the cobalt complex of the BPMB ligand has a distorted octahedral configuration. These complexes can catalyze the transfer hydrogenation reaction of simple olefins with good to excellent yields, and the Co-N4 complexes are more effective than the Co-N3 complex.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Qi-Jun Yao, Fan-Rui Huang, Jia-Hao Chen, Ming-Yu Zhong, Bing-feng Shi
Summary: In recent years, the merging of electrosynthesis with 3d metal catalyzed C-H activation has been developed as an effective technique in organic synthesis. However, an enantioselective version of this technique is still challenging. This study presents the first electrooxidative cobalt-catalyzed enantioselective C-H/N-H annulation with olefins at room temperature. The mechanism of the reaction was elucidated through cyclovoltametric studies and the preparation of cobaltacycle intermediates.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Organic
Sheng Zhang, Michael Findlater
Summary: This review focuses on cobalt-catalyzed alkene isomerization, including positional isomerization, geometric isomerization, and cycloisomerization. Three main types of reaction mechanism have been discussed to help the reader better understand and make meaningful comparisons.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Multidisciplinary
Liming Tan, Keyang Wu, Gang Li
Summary: In this study, a bioinspired cobalt catalyst was reported to efficiently catalyze the intermolecular cyclopropanation of various terminal olefins. The catalyst system is easy to operate and works under mild conditions, producing cyclopropane products with remarkable yields in a short reaction time. Preliminary mechanistic studies suggested the involvement of cobalt carbene radical species during the reaction.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Wei Hang, Nianjie Liang, Yuzhou Liu, Chanjuan Xi
Summary: A cobalt-catalyzed regioselective carboxylation reaction has been developed, allowing the conversion of aryl bromides with acrylates and carbon dioxide to valuable carboxylic acids. This method exhibits high regioselectivity and functional-group compatibility, providing an important strategy for the synthesis of organic acids.
Article
Chemistry, Organic
Fu-Yu Li, Bei Wang, Hong Xu, Yao Xiao, Dong-Wei Huang, Ji-Yu Wang
Summary: A series of synthetically challenging oxazolidinone compounds were successfully synthesized via a regioselective radical addition reaction of azonaphthalenes. The development of an iron-catalyzed reduction radical cascade strategy was carried out for the construction of poly-substituted oxazolidinones, particularly the synthesis of complex spiro oxazolidinones, which was of significant importance. Furthermore, the products could also be transformed into unreported and valuable oxadiazin-2-one and β-hydroxyhydrazine compounds.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Lijun Chang, Cheng Cai, Ran Chen, Jianhui Chen, Yanshu Luo, Yuanzhi Xia
Summary: The ligand-controlled cobalt-catalyzed isomerization and reductive C-O bond cleavage of allylic ethers are reported in this paper. With an amido-diphosphine ligand (PNP), the isomerization reaction proceeds smoothly, resulting in a series of trisubstituted enol ethers with high stereoselectivity. By using a phosphine-amido-oxazoline ligand (PAO), the reaction switches to reductive C-O bond cleavage in the presence of HBpin. Preliminary mechanistic studies suggest that both reactions proceed through cobalt-hydride mediated alkene insertion to form an alkylcobalt species, which is then selectively eliminated by the ligand.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Physical
Manoj Kumar Sahoo, Dongwook Kim, Sukbok Chang, Jung-Woo Park
Summary: This study demonstrates the regioselective migratory hydrofunctionalization of alkynes to produce alpha-vinylsilanes and alpha-vinylgermanes using a cobalt hydride based system. The mechanism of alkyne pi-bond migration by the cobalt hydride species is supported by both experimental and computational studies, which elucidates the unique alpha-vinyl selectivity.
Article
Chemistry, Multidisciplinary
Hyung-Joon Kang, Changseok Lee, Sungwoo Hong
Summary: Kinetic resolution is a powerful strategy for isolating enantioenriched compounds from mixtures, and the development of selective catalytic processes is an active research area. In this study, a nickel-catalyzed kinetic resolution of racemic alpha-substituted unconjugated carbonyl alkenes was achieved through enantio-, diastereo-, and regioselective hydroamination, resulting in chiral alpha-substituted butenamides and syn-beta(2,3)-amino acid derivatives with high enantiomeric purity (up to 99% ee) and selectivity factor up to >684. The unique structure of the chiral nickel complex plays a key role in the efficient kinetic resolution and enantioselective bond construction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Jinglin Qu, Zijuan Yan, Xuchao Wang, Jun Deng, Feipeng Liu, Zi-Qiang Rong
Summary: Aryl ketones, an important class of organic compounds, are widely used in the synthesis of pharmaceuticals, biologically active molecules, and functional materials. This study presents a facile synthetic method for the construction of aryl ketones through Ni-catalyzed cross coupling of epoxides with aryltriflates, resulting in highly regioselective conversion with good yields in a redox neutral manner.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Naoki Kimura, Shiori Katta, Yoichi Kitazawa, Takuya Kochi, Fumitoshi Kakiuchi
Summary: A new method for the C-H homoallylation reaction of aromatic ketones with methylenecyclopropanes using a catalytic amount of Fe(PMe3)(4) was reported, yielding selectively ortho-homoallylated aromatic ketones through regioselective scission of the three-membered rings. The homoallylated products are suitable for further modifications, leading to functionalized 1,2-dihydronaphthalenes.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Chenguang Liu, Mingyang Wang, Shihan Liu, Yujie Wang, Yong Peng, Yu Lan, Qiang Liu
Summary: The article reports on the non-noble metal-catalyzed asymmetric hydrogenation of N-heteroaromatics, quinolines. A new chiral pincer manganese catalyst showed outstanding catalytic activity in the reaction, producing high yields and enantioselectivities. The precise regulation of enantioselectivity was ensured by a pi-pi interaction, achieving competitive turnover numbers with noble metal catalysts.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Zhihui Shao, Shanshan Yuan, Yibiao Li, Qiang Liu
Summary: This study presents an efficient and sustainable synthetic route for the production of formaldehyde from renewable feedstock. The method involves the dehydrogenative cyclization of methanol as a formaldehyde surrogate, using a novel manganese catalyst, to synthesize N-heterocycles. The transformation shows high selectivity in trapping formaldehyde and avoids unwanted side reactions. Additionally, this method is successfully applied to the synthesis of C-13-labeled N-heterocycles.
CHINESE JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Organic
Jian Li, Yang Liu, Zebin Chen, Jiaming Li, Xiaoliang Ji, Lu Chen, Yubing Huang, Qiang Liu, Yibiao Li
Summary: A method for obtaining substituted thiophenes with functional potential through metal-free dehydration and sulfur cyclization was described. The reaction of alkynols with elemental sulfur (S-8) or EtOCS2K yielded moderate-to-good yields. The method showcased the base-free generation of a trisulfur radical anion (S-3(center dot-)) and its addition to alkynes as an initiator. This research broadens the applications of S-3(center dot-) in the synthesis of sulfur-containing heterocycles.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Mingyan Ding, Ze-Xin Zhang, Thomas Q. Davies, Michael C. Willis
Summary: A new N-silyl sulfinylamine reagent has been developed for the rapid synthesis of a wide range of (hetero)aryl, alkenyl, and alkyl primary sulfinamides, which can be further converted to NH-sulfonimidamides. This two-step sequence is straightforward and provides a modular approach for the synthesis of NH-sulfonimidamides with flexibility in reaction components.
Article
Chemistry, Multidisciplinary
Chenguang Liu, Mingyang Wang, Yihan Xu, Yibiao Li, Qiang Liu
Summary: This study presents a Mn-catalyzed asymmetric hydrogenation of 3H-indoles, achieving high yields and enantioselectivities. The use of manganese catalyst allows for the compatibility of acid-sensitive functional groups, expanding the scope of this transformation and highlighting the uniqueness of earth-abundant metal catalysis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Ze-Xin Zhang, Michael C. Willis
Summary: Sulfonamides, with their unique structure and properties, play a significant role in designing bioactive molecules. Mono aza variants, sulfonimidamides, and double aza analogs, sulfondiimidamides, are two functional groups. However, the synthesis of sulfondiimidamides is challenging, and their assembly and modification can be achieved through specific methods.
Article
Chemistry, Multidisciplinary
Ze-Xin Zhang, Charles Bell, Mingyan Ding, Michael C. Willis
Summary: Sulfondiimidamides, the double aza-variants of sulfonamides, are rarely reported due to their poor synthetic accessibility. In this study, a two-step synthesis of sulfondiimidamides was described, using a hypervalent iodine-mediated amination as the key step. The method demonstrated operational simplicity, broad scope, and concise nature, making it attractive for discovery chemistry applications.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Yujie Wang, Shihan Liu, Haobo Yang, Hengxu Li, Yu Lan, Qiang Liu
Summary: Research shows that a higher efficiency can be achieved by substituting an N-M' group (M' = alkali metals) for the N-H moiety using a large excess of metal alkoxides (M'OR), but the metal-hydride amidate intermediate has not yet been isolated. Furthermore, it is found that M/NM' bifunctional catalysis is superior to classic M/NH bifunctional catalysis in hydrogenation reactions.
Article
Chemistry, Multidisciplinary
Zeyuan Wei, Hengxu Li, Yujie Wang, Qiang Liu
Summary: The reactivity of metal-hydride complexes can be controlled by modifying ancillary ligands. In this study, a versatile and efficient NHC-based NNC-pincer Mn catalyst was designed to enhance the hydride-donor ability and reduce steric hindrance. The newly developed catalyst showed higher activity than the corresponding NNP-pincer Mn catalyst, enabling successful hydrogenation of a wide range of polar unsaturated compounds under mild conditions. This work presents a rare example of a general phosphine-free Mn-catalyzed hydrogenation system.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Bingxue Liu, Deguang Liu, Xianle Rong, Xi Lu, Yao Fu, Qiang Liu
Summary: A ligand-controlled stereoselective C-alkyl glycosylation reaction was reported for the synthesis of 2-deoxy-beta-C-alkyl glycosides from readily available glycals and alkyl halides. The method exhibits broad substrate scope and excellent diastereoselectivity under very mild conditions. In addition, a stereodivergent synthesis of 2-deoxy-C-ribofuranosides was achieved using different chiral bisoxazoline ligands.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Bingxue Liu, Qiang Liu
Summary: Cobalt-catalyzed hydroalkylation of alkenes and alkynes is an efficient method for selective formation of C-C bonds. Significant progress has been made in the past five years, covering different reaction mechanisms.
Article
Chemistry, Multidisciplinary
Bingxue Liu, Qiang Liu
Summary: In this study, we report a method for the reductive deoxygenation of ketones using a cobalt/Lewis acid catalyst and H-2 as the reductant. We discovered that the newly developed catalyst exhibits dual hydrogenation activities for both ketones and alkenes under the same reaction conditions. This method shows a broad substrate scope, excellent functional-group compatibility, and potential applicability.
CHINESE JOURNAL OF CHEMISTRY
(2023)
Review
Chemistry, Organic
Liu Chenguang, Liu Qiang
Summary: The use of earth-abundant metal catalysts for asymmetric hydrogenation reactions has significant implications for sustainable synthesis of chiral nitrogen-containing fine chemicals, replacing the reliance on noble-metal catalysts.
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Bingxue Liu, Yibiao Li, Qiang Liu
Summary: This study reports a novel cooperative cobalt/Lewis acid (LA)-catalyzed reductive etherification method using H-2 as the reductant, which can efficiently synthesize various ether molecules. The method demonstrates high selectivity and wide scope of application.
Article
Chemistry, Physical
Xufang Liu, Qiang Liu
Summary: Catalytic asymmetric olefin isomerization is an important reaction for the synthesis of enantioenriched olefinic compounds with biological activity and pharmaceutical value. Highly selective catalytic methods have been developed for the synthesis of challenging chiral olefins. This perspective summarizes the major advances in this field and discusses the mechanisms, scope and limitations, and opportunities for further development.