Article
Chemistry, Multidisciplinary
Shiyao Liu, Yoshiaki Tanabe, Shogo Kuriyama, Ken Sakata, Yoshiaki Nishibayashi
Summary: In recent years, significant progress has been made in the development of transition metal-catalyzed enantioselective propargylic substitution reactions. However, until now, no successful example with phosphorus-centered nucleophiles has been reported. This study presents the first successful example of ruthenium-catalyzed enantioselective propargylic substitution reactions using propargylic alcohols as substrates and diarylphosphine oxides as phosphorus-centered nucleophiles, providing a new method for preparing chiral phosphorus-containing organic compounds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Zhiheng Li, Danran Li, Huaming Xiang, Jian Huang, Yinuo Zheng, Cuiju Zhu, Xiuling Cui, Chao Pi, Hao Xu
Summary: In this study, a highly enantioselective propargylic substitution reaction of anthrones with propargylic esters using copper salts with chiral N, N, P-ligand was disclosed. This strategy shows broad substrate compatibility, mild reaction conditions, excellent yields with remarkable enantioselectivity, and enables the synthesis of diverse products.
CHINESE CHEMICAL LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Shiyao Liu, Yoshiaki Tanabe, Shogo Kuriyama, Ken Sakata, Yoshiaki Nishibayashi
Summary: In this study, propargylic substitution reactions using ruthenium and copper catalysis with N-monosubstituted hydrazones as ambident nucleophiles were investigated. It was found that N-monosubstituted hydrazones exhibited different reactivities depending on the catalytic system, resulting in either propargylic alkylated or aminated products. DFT calculations were used to study the reaction pathways and further transformation of the products yielded multisubstituted pyrazoles in good to high yields.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Editorial Material
Chemistry, Multidisciplinary
Shiyao Liu, Yoshiaki Tanabe, Shogo Kuriyama, Ken Sakata, Yoshiaki Nishibayashi
Summary: The cover of this issue features the research on the propargylic substitution reaction of propargylic alcohol with an N-monosubstituted hydrazone, where the nucleophilicity of the hydrazone is controlled by the choice of catalytic system. The full article can be accessed at 10.1002/chem.202103287.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Katsuki Endo, Daiki Tomon, Satoru Arimitsu
Summary: This paper reports the highly enantioselective alpha-fluorination of both cyclic and acyclic beta-dicarbonyl compounds, achieving yields of 50-99% with excellent enantioselectivity (up to 98% ee). By using beta,beta-diaryl serines as primary amine organocatalysts and adding alkali carbonates (such as Na2CO3 or Li2CO3), the reaction could be conducted with only 1.1 equiv of Selectfluor.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Aleria Garcia-Roca, Raul Perez-Soto, Georgiana Stoica, Jordi Benet-Buchholz, Feliu Maseras, Arjan W. Kleij
Summary: Metal-catalyzed propargylic transformations are a powerful tool in organic synthesis for forming new carbon-carbon and carbon-heteroatom bonds. However, there is limited knowledge about the mechanistic intricacies of asymmetric propargylic reactions with challenging heteroatom substitution, presenting an inspiring challenge. This study presents a detailed mechanistic analysis of a propargylic sulfonylation reaction promoted by a chiral Cu catalyst through experimental techniques and computational studies. Surprisingly, the enantio-discriminating step was found to be the proto-demetalation step, rather than the coupling between the nucleophile and the propargylic precursor.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Multidisciplinary Sciences
Jiayin Zhang, Xihao Chang, Xianghong Xu, Hongyi Wang, Lingzi Peng, Chang Guo
Summary: This study demonstrates the nickel-catalyzed dienylation and enantioselective allenylation of phosphine oxides, showing high selectivity in terms of chemo-, regio-, and enantioselectivity.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Chengyu Yu, Guoren Yue, Penji Yan, Hai Song, Hucheng Shi, Yangfei Wei, Zhengen Song, Xin Jia
Summary: A novel synthesis of highly functionalized dihydrofuranyl alcohols has been developed through a tandem process, resulting in good yields of up to 97.1%.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Wen-Ya Lu, Yong You, Ting-Ting Li, Zhen-Hua Wang, Jian-Qiang Zhao, Wei-Cheng Yuan
Summary: A new method for synthesizing allenyl thioether compounds via CuI-catalyzed decarboxylative thiolation of terminal alkyne-substituted cyclic carbonates/carbamates has been successfully developed. A variety of hydroxymethyl- and aminomethyl-containing allenyl thioethers were obtained in good to excellent yields under mild conditions. The copper-allenylidene intermediate plays a crucial role in the decarboxylative thiolation reaction.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Juanjuan Wu, Hongli Wu, Xinzhi Li, Xinyu Liu, Qian Zhao, Genping Huang, Chun Zhang
Summary: The study presents a copper-catalyzed highly selective protoboration reaction that can suppress defluorination and provide CF3-containing borated reagents. Functional group tolerance of this reaction is well demonstrated, with the products serving as versatile precursors for various transformations. By using a chiral diphosphine ligand, allylic boron reagents with a CF3-containing chiral center were synthesized for the first time. Additionally, in-depth DFT calculations were conducted to understand the mechanism behind the inhibition of defluorination.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Aabid A. Wani, Kriti Mehta, Rajeswara Reddy, Prasad V. Bharatam
Summary: This article reports the 1,1-diaminoazine-catalysed Michael addition reaction of malonates with nitro-olefins. The bifunctional nature of the catalyst facilitates the C-C bond formation.
NEW JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Aitor Bermejo-Lopez, Wei-Jun Kong, Pedro J. Tortajada, Daniels Posevins, Belen Martin-Matute, Jan-E Backvall
Summary: A novel iron-catalyzed borylation reaction of propargylic acetates leading to allenylboronates has been developed. This method allows the preparation of di-, tri-, and tetrasubstituted allenylboronates at room temperature with good functional group compatibility. Stereochemical studies show that an anti-S(N)2' displacement of acetate by boron occurs, allowing chirality transfer to yield enantiomerically enriched allenylboronates.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Multidisciplinary Sciences
Xiang Pu, Qiu-Di Dang, Lei Yang, Xia Zhang, Dawen Niu
Summary: The authors report a doubly-stereoconvergent, Cu/Mg-catalyzed asymmetric propargylic substitution reaction that can selectively construct products with vicinal congested stereocenters. This reaction uses readily available starting materials, environmentally friendly catalysts, and has a broad substrate scope.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Yujie He, Hao Yin, Yifeng Wang, Mingming Chu, Yiming Li
Summary: We have developed an efficient method for oxidative alpha-hydroxylation of beta-keto esters. The method uses ethylenediamine-copper(ii) as a catalyst for beta-keto esters activation and visible light as the driving force to generate more active singlet oxygen. This method provides a series of alpha-hydroxy beta-keto esters in excellent yields within a short time and with low photosensitizer and catalyst loading. The gram-scale synthesis demonstrates the practical utility of this protocol.
Article
Chemistry, Applied
Biao Zhang, Xu-Heng Yang, Jian Huang, Cheng-an Tao, Jianfang Wang
Summary: A cobalt-catalyzed cyclization reaction was achieved using various 1,3-dicarbonyl compounds and halogenated N-allyl ynamides under alkaline conditions, leading to the synthesis of N-heterocycles of different sizes. The reaction exhibited broad substrate scope and tolerance towards various functional groups, enabling the selective synthesis of 5-, 6-, and 7-membered ring N-heterocycles via cobalt catalysis.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
