Article
Chemistry, Multidisciplinary
Sa-Na Yang, Shao-Han Sun, Chang -Hui Liu, Xiang -Ting Min, Boshun Wan, Ding -Wei Ji, Qing-An Chen
Summary: A regiodivergent hydrophosphorylation of enynes with phosphites has been developed using earth-abundant nickel catalyst. The manipulation of regioselectivity can be achieved by regulating the insertion order of alkyne bonds with (RO)(2)P(O)-Ni-H or R2P(O)O-Ni-H species, respectively. This research highlights the ability to access different regioisomers by diverting common elementary reaction steps.
CHINESE CHEMICAL LETTERS
(2023)
Article
Chemistry, Organic
Binlin Zhao, Yukun Zheng, Tianxiang Zhu, Mengning Wang, Minyan Wang, Mengtao Ma
Summary: In this study, a direct copper-catalyzed fluorocarboalkynylation of readily available alkynes was achieved with good yields and operational simplicity. Mechanistic experiments and DFT calculations indicated the involvement of a radical-mediated process in the catalytic cycle.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Multidisciplinary
Haifeng Chen, Chen Zhu, Huifeng Yue, Magnus Rueping
Summary: In this study, a nickel-catalyzed, three-component reductive protocol for group 14 element hetero-difunctionalization of 1,3-enynes using electrochemistry is described. The method is mild, selective, and general, allowing for the silyl-, germanyl-, and stannyl-alkylation of enynes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Feilong Sun, Chengxi Yang, Jie Ni, Gui-Juan Cheng, Xianjie Fang
Summary: A regiodivergent nickel-catalyzed hydrocyanation of 1-aryl-4-silyl-1,3-diynes is reported, where appropriate ligands result in high yields and regioselectivities of two different enynyl nitriles. DFT calculations show that different ligands lead to diverse alkyne insertion modes, impacting the regioselectivity. The synthetic value of cyano-containing 1,3-enynes is demonstrated through downstream transformations.
Article
Chemistry, Organic
Ariel L. Burgio, Nicklas W. Buchbinder, Webster L. Santos
Summary: A facile method for the synthesis of (Z)-1,3-enynes is achieved through sequential copper-catalyzed regio- and stereoselective borylation-protodeboronation of 1,3-diynes. Pinacolborane, copper(II) acetate, and Xantphos are utilized as the ligand to efficiently introduce hydrogen and Bpin in a cis fashion, followed by rapid hydrolysis with water. The reaction exhibits wide substrate scope and proceeds in a chemoselective manner.
Review
Chemistry, Multidisciplinary
Sebastian M. Weber, Gerhard Hilt
Summary: This review outlines recent advances in chemo-, regio-, and stereoselective (cross-) dimerization of terminal alkynes to generate 1,3-enynes using various iron and cobalt catalysts with different oxidation states. The choice of ligands plays a crucial role in determining the stereoselectivity of the reaction, resulting in different product configurations.
FRONTIERS IN CHEMISTRY
(2021)
Article
Chemistry, Physical
Jianyu Xu, Olivia P. Bercher, Michael R. Talley, Mary P. Watson
Summary: The development of mild, nickel-catalyzed cross-couplings for the preparation of highly enantioenriched products, including those with quaternary stereocenters, has expanded the synthetic toolbox. This perspective highlights the use of convenient and functional-group-tolerant organoboron reagents, as well as the discoveries of activating groups and conditions that have led to highly stereospecific reactions. Emphasis is placed on mechanistic understanding and controlling inversion vs retention pathways, while also discussing limitations and future development opportunities.
Article
Chemistry, Multidisciplinary
Yanhua Hu, Zhenfeng Zhang, Yangang Liu, Wanbin Zhang
Summary: Asymmetric hydrogenation is an effective method for preparing single enantiomer compounds, but the chemoselective and enantioselective hydrogenation of relatively inert unsaturated groups in substrates with multiple unsaturated bonds remains a challenge. A highly selective hydrogenation method for producing chiral propargylamines and enabling useful chemical transformations has been reported.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Tzu-Yu Yu, Haobo Pang, Yilin Cao, Fabrice Gallou, Bruce H. Lipshutz
Summary: A new method of C-S coupling based on nickel catalysis in water with micellar catalysis has been reported, showing high isolated yields under mild conditions. It offers potential for scalability and low residual metal content, making it applicable to pharmaceutical synthesis targets. The associated low E Factor also suggests it may be a more attractive option compared to current methods using unsustainable Pd catalyst loadings.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Ren-Xiao Liang, Heng-Wei Tang, Jia-Liang Liu, Jian-Feng Xu, Ling-Jia Chen, Yi-Xia Jia
Summary: A highly enantioselective cobalt-catalyzed desymmetrizing reductive cyclization of alkynyl cyclodiketones has been developed. This reaction utilizes HBpin as a reducing agent and ferrocene-based PHOX as a chiral ligand to achieve moderate to excellent yields of polycyclic tertiary allylic alcohols with excellent enantioselectivities (up to 99%). The reaction demonstrates broad substrate scope, high functional group compatibility, and a proposed CoH-catalyzed pathway.
Article
Chemistry, Multidisciplinary
Herong Chen, Zhijun Zhou, Wangqing Kong
Summary: The new nickel-catalyzed direct coupling reaction can directly convert alkenes and methanol into valuable allylic alcohols with good yield and selectivity, and has a wide range of applicable substrates. This method has also been successfully applied to the synthesis of [5,6]-bicyclic hemiacetals.
Article
Chemistry, Organic
Hong-Liu Xiao, Gang Zhang, Rui-Qiang Luo, Qing-Han Li
Summary: A catalytic synthesis of conjugated enynes was developed using NiCl2(PPh3)(2)/XantPhos catalysts in DME solvent, by the cross-coupling of terminal alkynyl halides with alkenylaluminum reagents. This method is simple and efficient, providing high yields of conjugated enynes and is suitable for a variety of aryl alkynyl halides.
Article
Chemistry, Organic
Zhantao Yang, Zhiqiang Yu, Yulin He, Wei Feng, Yinchao Zhang, Junjie Wang, Xiangtao Kong, Chun-Hua Yang
Summary: A Rh-catalyzed regioselective, stereoselective carbocyclization/borylation reaction of acrylate-containing 1,6-enynes was developed, enabling the synthesis of versatile and densely functionalized pyrrolidine compounds. The reaction allows for the formation of pyrrolidines with either (Z) or uncommon (E) geometry at the double bond, depending on the substituent on the alkyne, with sterically hindered and conjugative aryl groups favoring the latter configuration. The reaction also leads to the formation of a tetrasubstituted vinyl boronate, containing an all-carbon quaternary stereocenter.
Article
Chemistry, Organic
Ran Ding, Ya-Li Liu, Hui Hao, Chuan-Yi Chen, Lei Liu, Nian-Shou Chen, Yu Guo, Pei-Long Wang
Summary: A copper(I)-catalyzed sulfonylation-cyclization method has been developed for the transformation of 1,5-dienes with sulfonyl chlorides. The reaction exhibits a wide substrate scope and excellent regioselectivity, resulting in the formation of derivatized 1,5-dihydro-2H-pyrrol-2-one scaffold in one pot.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Applied
Bohdan Biletskyi, Lingyu Kong, Alphonse Tenaglia, Herve Clavier
Summary: A novel cobalt-catalyzed hydroalkynylation reaction was discovered, enabling the synthesis of enynes from vinylaziridines. The study showed that the cobalt-catalyzed hydroalkynylation reaction is mainly applicable to phenylacetylene derivatives, with branched and linear enynes formed in equimolar proportions in most cases.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
