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
Ruo-Qing Wang, Chong Shen, Xiang Cheng, Xiu-Qin Dong, Chun-Jiang Wang
Summary: In this study, copper-catalyzed asymmetric propargylic substitution was successfully achieved using salicylaldehyde-derived imine esters and propargylic carbonates, resulting in a wide range of chiral amino acid derivatives containing propargylic groups. The ortho-hydroxy group of the salicylaldehyde-derived imine esters played a crucial role in increasing reactivity and stabilizing the azomethine ylide.
CHEMICAL COMMUNICATIONS
(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, 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
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
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, Organic
Dandan Sun, Thayalan Rajeshkumar, Yifan Li, Jiaxin Xu, Runkai Chen, Zhaohua Wan, Zongchao Lv, Laurent Maron, Yi-Hung Chen
Summary: Transition-metal-catalyzed cross-coupling of propargylic electrophiles and Grignard reagents provides useful synthetic intermediates. However, few examples exist for the conversion of propargylic derivatives into propargyl compounds due to the challenging regioselectivity. We demonstrate a regioselective and stereospecific propargylation of Grignard reagents using LaCl3.2LiCl as a catalyst in the absence of a ligand.
Article
Chemistry, Organic
Rina Muto, Kenji Nagata, Yoshiki Nakazumi, Kaho Nakamura, Satoshi Ueno
Summary: The Pd/PMe3-catalyzed allylation reaction of 1-(cyanomethyl)naphthalenes with allyl acetates showed para-selectivity instead of aregioselectivity. This reaction proceeds through ligand attack on the para-carbon of the arenes, which is electronically enriched by a cyano-stabilized α-carbanion. This leads to the formation of (p-allyl)palladium intermediate and a 1,5-hydrogen shift of the parahydrogen.
Article
Chemistry, Multidisciplinary
Antonio Arcadi, Giancarlo Fabrizi, Andrea Fochetti, Francesca Ghirga, Antonella Goggiamani, Antonia Iazzetti, Federico Marrone, Giulia Mazzoccanti, Andrea Serraiocco
Summary: The palladium-catalyzed benzylic-like nucleophilic substitution of benzofuran-2-ylmethyl acetate with N, S, O and C soft nucleophiles was investigated, showing different catalytic systems have significant effects on the reaction outcome, with nucleophilic substitution only occurring at the benzylic position.
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
Jian Huang, Han-Han Kong, Si-Jia Li, Rui-Jin Zhang, Hao-Dong Qian, Dan-Ran Li, Jin-Yu He, Yi-Nuo Zheng, Hao Xu
Summary: The highly enantioselective copper-catalyzed propargylic amination of propargylic esters with amine hydrochloride salts using chiral N,N,P-ligands has been successfully developed. This method demonstrates a broad substrate scope and wide functional group tolerance, producing propargylic amines in good to excellent yields with high enantioselectivities (up to 99% ee). The approach was further validated by late-stage functionalization of marketed pharmaceuticals.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Shuting Zhang, Shuaijie Wu, Qiang Wang, Shiji Xu, Ying Han, Chao-Guo Yan, Junliang Zhang, Lei Wang
Summary: This article reports the first palladium-catalyzed asymmetric alleneamination of beta,gamma-unsaturated hydrazones with propargylic acetates. The reaction enables the efficient installation of various multisubstituted allene groups onto dihydropyrazoles in good yields with excellent enantioselectivities. The salient features of this reaction include readily available starting materials, a broad substrate scope, easy scale-up, mild reaction conditions, and versatile transformations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Multidisciplinary Sciences
Xihao Chang, Jiayin Zhang, Lingzi Peng, Chang Guo
Summary: The study introduces an enantioselective nickel/Lewis acid-catalyzed asymmetric propargylic substitution reaction for the synthesis of structurally diverse natural products from simple achiral materials under mild conditions. The addition of a Lewis acid cocatalyst is crucial for enhancing the efficiency of the transformation and the strategy is powerful for collectively synthesizing seven biologically active compounds.
NATURE COMMUNICATIONS
(2021)
