Nickel-catalyzed formation of quaternary carbon centers using tertiary alkyl electrophiles
Transformation of sterically hindered tertiary alkyl electrophiles under nickel-catalyzed conditions to forge C(sp 3 )-C bonds and simultaneously create challenging all-carbon quaternary centers has received growing attention in the recent years. The unique nature of nickel featuring flexible oxidat...
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| Published in | Chemical Society reviews Vol. 5; no. 6; pp. 4162 - 4184 |
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| Main Authors | , , , , , |
| Format | Journal Article |
| Language | English |
| Published |
England
Royal Society of Chemistry
21.03.2021
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| Subjects | |
| Online Access | Get full text |
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| Summary: | Transformation of sterically hindered tertiary alkyl electrophiles under nickel-catalyzed conditions to forge C(sp
3
)-C bonds and simultaneously create challenging all-carbon quaternary centers has received growing attention in the recent years. The unique nature of nickel featuring flexible oxidation states ranging from Ni
0
to Ni
IV
, allows the effective activation of tertiary alkyl electrophiles through ionic (2e) or radical pathways. In nickel-catalyzed coupling of tertiary alkyl electrophiles, the competitive β-H elimination upon the resulting alkyl-Ni intermediate is relatively slow, thus benefiting the C-C bond forming process. Meanwhile, nickel-catalyzed radical addition of tertiary alkyl electrophiles to unsaturated C-C bonds has also advanced rapidly due to the successful incorporation of carboxylic acid and alcohol derivatives as radical precursors, and more importantly due to further interception of the intermediate radical adducts with nucleophiles and electrophiles to accomplish three-component cascade reactions. This review highlights these state-of-the-art nickel-catalyzed transformations of tertiary electrophiles, organized by reaction types with emphasis on the reaction mechanisms.
This review provides a comprehensive summary of recent advances in nickel-catalyzed reactions employing tertiary alkyl electrophiles for the construction of quaternary carbon centers. |
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| Bibliography: | Weichao Xue obtained his BS (w/Dr. Feng Shi) and MS (w/Prof. Hegui Gong) at Henan University and Shanghai University, respectively. Subsequently, he moved to Technische Universität Berlin, where he obtained his PhD (w/Prof. Martin Oestreich) with summa cum laude. Currently, he is a postdoctoral research fellowship (w/Prof. Jonathan Nitschke) at the University of Cambridge, funded by Deutsche Forschungsgemeinschaft (DFG). He is interested in exploring the novel applications of first-row transition metals, e.g., in cross-coupling, organosilicon chemistry and metal-organic nanocapsules. Xianghua Tao obtained his Bachelor of Science at Huainan Normal University, and Master's degree at East China Normal University. He is currently a PhD candidate under the supervision of Prof. Hegui Gong at Shanghai University. His research focuses on nickel-catalyzed reductive formation of amino acids. Zhigang Yin obtained his BS (w/Prof. Yuhua Liu) at Zhengzhou University in 1985. He then obtained his MS and PhD (w/Prof. Defeng Zhao) at the State Key Laboratory of Fine Chemical Engineering, Dalian University of Technology. He is now a full professor at Zhengzhou University of Light Industry and engages in teaching and research in organic chemistry including chiral cyclopalladium compounds and development of new cosmetics raw materials. Xuan Wang obtained his Bachelor of Science at Shanxi University. After receiving his PhD under the supervision of Prof. Hegui Gong at Shanghai University, he moved to the U.S. to continue his research. At present, Xuan is a postdoctoral research associate with Prof. Michel R. Gagné at the University of North Carolina at Chapel Hill. His research focuses on nickel-catalyzed coupling reactions and Lewis acid-catalyzed deoxygenation of cellulosic feedstocks. Xiao Jia completed his BS and MS in chemistry at Shanghai University under the supervision of Prof. Hegui Gong. In 2016, he joined the research group of Prof. Chris Meier at Universität Hamburg and recently obtained his PhD with summa cum laude. Afterwards, Xiao decided to stay in the same laboratory to continue his research on medicinal chemistry as a postdoctoral researcher. He is currently focused on the development of nucleoside triphosphate prodrugs. Hegui Gong obtained his PhD degree from the University of Texas at Austin (with Prof. Michael J. Krische). After postdoctoral research at the University of North Carolina at Chapel Hill (with Prof. Michel R. Gagné), he was appointed as a full professor at Shanghai University (China) in 2008. His research interest has been centered on Ni-catalyzed C-C bond formation and H-bond mediated supramolecular chemistry. ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 14 content type line 23 |
| ISSN: | 0306-0012 1460-4744 1460-4744 |
| DOI: | 10.1039/d0cs01107j |