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DOI: 10.1055/a-1998-7007
Bromine-Radical-Mediated Bromoallylation of C–C Unsaturated Bonds: A Facile Access to 1,4-, 1,5-, 1,6-, and 1,7-Dienes and Related Compounds
This work was supported by a Grant-in-Aid B for Scientific Research from the Japan Society for the Promotion of Science (JSPS). I.R. acknowledges funding from the National Science and Technology Council (NSTC) (MOST-108-2113-M-009-007) and the Center for Emergent Functional Matter Science at National Yang Ming Chiao Tung University (NYCU) for additional support.
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Abstract
The radical bromoallylation of alkynes, allenes, and vinylidene cyclopropanes proceeds efficiently in the presence of a radical initiator to give 2-bromo-substituted 1,4-, 1,5-, and 1,6-diene derivatives, respectively. Three-component reactions comprised of allenes, electron-deficient alkenes, and allyl bromides give 1,7-dienes in good yields. The bromoallylation of an arylalkene can override β-scission of the bromine radical from β-bromoalkyl radicals to give 5-bromoalkenes, whilst the bromoallylation of vinylcyclopropanes is accompanied by 5-exo ring closure to give 1-(bromomethyl)-2-vinylcyclopentane derivatives in good yields. All of the products contain a reactive vinyl bromide moiety, which can be readily functionalized by Pd-catalyzed cross-coupling and radical cascade reactions.
1 Introduction
2 Synthesis of 1,4-Dienes by Bromoallylation of Acetylenes
3 Synthesis of 1,5-Dienes by Bromoallylation of Allenes
4 Synthesis of 1,6-Dienes by Bromoallylation of Methylenecyclopropanes
5 Synthesis of 1,7-Dienes by Bromoallylation of Allenes and Electron-Deficient Alkenes
6 Bromoallylation of Arylalkenes and Vinylcyclopropanes
7 Conclusion
Key words
dienes - radical allylation - Br radical - allyl bromides - alkynes - allenes - methylenecyclopropanes - vinylcyclopropanesPublication History
Received: 07 November 2022
Accepted after revision: 15 December 2022
Accepted Manuscript online:
15 December 2022
Article published online:
13 January 2023
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