Abstract
AbstractControlling the reactivity of reactive intermediates is essential to achieve selective transformations. Due to the facile 1,5-hydrogen atom transfer (HAT), alkoxyl radicals have been proven to be important synthetic intermediates for the δ-functionalization of alcohols. Herein, we disclose a strategy to inhibit 1,5-HAT by introducing a silyl group into the α-position of alkoxyl radicals. The efficient radical 1,2-silyl transfer (SiT) allows us to make various α-functionalized products from alcohol substrates. Compared with the direct generation of α-carbon radicals from oxidation of α-C-H bond of alcohols, the 1,2-SiT strategy distinguishes itself by the generation of alkoxyl radicals, the tolerance of many functional groups, such as intramolecular hydroxyl groups and C-H bonds next to oxygen atoms, and the use of silyl alcohols as limiting reagents.
Publisher
Springer Science and Business Media LLC
Subject
General Physics and Astronomy,General Biochemistry, Genetics and Molecular Biology,General Chemistry
Reference52 articles.
1. Smith, M. B. March’s Advanced Organic Chemistry: Reactions, Mechanisms, and Structure 7th edn (Wiley, 2013).
2. Fu, G. C. Transition-metal catalysis of nucleophilic substitution reactions: a radical alternative to SN1 and SN2 processes. ACS Cent. Sci. 3, 692–700 (2017).
3. Lo, J. C. et al. Fe-catalyzed C-C bond construction from olefins via radicals. J. Am. Chem. Soc. 139, 2484–2503 (2017).
4. Yi, H. et al. Recent advances in radical C-H activation/radical cross-coupling. Chem. Rev. 117, 9016–9085 (2017).
5. Renaud, P. & Sibi, M. P. (eds). Radicals in Organic Synthesis (Wiley-VCH, 2001).
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