New progress in asymmetric catalytic conversion of olefins

Recently, the research group of Professor Chen Yifeng from the School of Chemistry and Molecular Engineering of East China University of Science and Technology and the Joint Research Center of Feringa Nobel Prize Scientists has made new research progress in the field of asymmetric catalytic conversion of alkenes
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The related research results were published in German Applied Chemistry under the title "Ni-catalyzed enantioselective reduction of carbamoyl-alkylation of internalenes"
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In recent years, transition metal-catalyzed intramolecular asymmetric bifunctional cyclization of olefins has gradually become one of the most important methods to construct chiral cyclic frameworks
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Among them, nickel-catalyzed asymmetric reduction and bifunctionalization of alkenes can not only avoid the use of organometallic reagents, but also successfully introduce C(sp3) coupling components that are prone to β-H elimination side reactions in palladium-catalyzed systems.
to the end of the alkene, so it has attracted much attention
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Currently, most studies focus on terminal alkenes substituted by electrophiles
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In contrast, the construction of two consecutive chiral centers through a nickel-catalyzed asymmetric difunctionalization strategy of internalenes still remains a great challenge
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The possible reasons are that the low reactivity of internal alkenes and the low affinity of internal alkenes to nickel catalysts further hindered the cyclization step of the reaction, and the easy homolysis of the alkyl nickel intermediates after cyclization increased the non-efficiency of the reaction.
Difficulty in regulating enantioselectivity
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Transition metal-catalyzed enantioselective cyclization of carbamoyl electrophiles, as one of the important methods for the synthesis of chiral lactams, has received extensive attention from chemists in recent years
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Based on the research interest of Prof.
Yifeng Chen's research group in the construction of multiple chiral centers based on the transition metal-catalyzed asymmetric bifunctionalization of olefins, through the further optimization of the chiral 8-quinolinimidazoline developed by the research group as the core skeleton Quinim ligand, Nickel-catalyzed asymmetric carbamoyl-alkylation of lactenes was achieved, providing a novel, mild and efficient method for the facile synthesis of γ-lactams containing continuous chiral centers
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In addition, the research group also cooperated with KN Houk's research group at the University of California, Los Angeles (UCLA) to perform DFT theoretical calculations on the role of Quinim ligands in the decision step of enantioselectivity and the reaction mechanism
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Theoretical calculations provide theoretical guidance for the reaction mechanism of nickel-catalyzed reductive coupling chemistry and the further design and development of Quinim chiral ligands
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Wu Xianqing, a postdoctoral fellow from the School of Chemical and Molecular Engineering, East China University of Science and Technology, and Aneta Turlik, a postdoctoral fellow from the University of California, Los Angeles (UCLA), are the co-first authors.
Professor KN Houk from UCLA and Professor Chen Yifeng from East China University of Science and Technology are the co-corresponding authors of this work.

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The research work has received the strong support and careful guidance of Professor Qu Jingping
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This research work has been supported by the Frontier Science Center for Materials Biology and Dynamic Chemistry of the Ministry of Education, the Feringa Joint Research Center for Nobel Prize Scientists, the National Natural Science Foundation of China, the Shanghai "Morning Star" Program, the Shanghai Natural Science Foundation, and the Central Universities Funds such as basic scientific research business fees and support from China Postdoctoral Science Foundation
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