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Synlett
DOI: 10.1055/a-2591-9299
DOI: 10.1055/a-2591-9299
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First-Row Transition-Metal Catalysis for Organic Synthesis
Regioselective Transformations of Unsaturated Systems Catalyzed by Low-Valent Nickel: Cycloaddition, Hydrosilylation, and Dicarbofunctionalization
This research was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (RS-2020-NR049543). G.H.K. is grateful for a postdoctoral fellowship supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (RS-2024-00452066). S.Y.H. also acknowledges the support by the Technology Innovation Program (RS-2024-00437259, development of additives for enhanced high-voltage stability and liquid electrolytes technology for application of mid-nickel cathode materials) funded by the Ministry of Trade, Industry and Energy (MOTIE, Korea). J.-U.R. acknowledges support from the UNIST Research Fund (1.130085.01).
Abstract
In this Account, we describe our recent research progress in the development of the functionalization of unsaturated substrates catalyzed by low-valent nickel. In particular, we discuss nickel-catalyzed azide–alkyne cycloaddition (NiAAC), [2 + 2 + 2] cycloaddition of diynes and nitriles, hydrosilylation of alkynes, and dicarbofunctionalization of 1,3-enynes. Moreover, we highlight our mechanistic studies aimed at elucidating catalytically active nickel intermediates, thereby contributing to the understanding and expansion of nickel-catalyzed synthetic methodologies.
1 Introduction
2 Nickel(0)-Catalyzed Cycloaddition Reactions
3 Nickel(I)-Catalyzed Hydrosilylation and Dicarbofunctionalization Reactions
4 Conclusion and Outlook
Key words
unsaturated systems - nickel - cycloaddition - hydrosilylation - dicarbofunctionalization - regioselectivity - reaction mechanismsPublication History
Received: 10 March 2025
Accepted after revision: 21 April 2025
Accepted Manuscript online:
21 April 2025
Article published online:
17 June 2025
© 2025. Thieme. All rights reserved
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