Abstract
AbstractThe introduction of chlorine atoms into organic molecules is fundamental to the manufacture of industrial chemicals, the elaboration of advanced synthetic intermediates and also the fine‐tuning of physicochemical and biological properties of drugs, agrochemicals and polymers. We report here a general and practical photochemical strategy enabling the site‐selective chlorination of sp3C−H bonds. This process exploits the ability of protonatedN‐chloroamines to serve as aminium radical precursors and also radical chlorinating agents. Upon photochemical initiation, an efficient radical‐chain propagation is established allowing the functionalization of a broad range of substrates due to the large number of compatible functionalities. The ability to synergistically maximize both polar and steric effects in the H‐atom transfer transition state through appropriate selection of the aminium radical has provided the highest known selectivity in radical sp3C−H chlorination.
Highlights
Chlorine-containing molecules are integral to all chemical disciplines (Scheme 1A).[1]
It has been estimated that the manufacture of >50% of industrial chemicals and >20% of pharmaceutical products requires at some point the introduction of a chlorine atom into a feedstock or an advanced building block, respectively.[2]
Overall, achieving high selectivity in radical sp3 C–H chlorination is still challenging because it requires fine control of the interplay between multiple factors that determine the reactivity of each individual sp3 C–H bond.[6]
Summary
Citation for published version (APA): Mcmillan, A., Siekowska, M., Lorenzo, P. D., Gransbury, G., Chilton, N., Salamone, M., Ruffoni, A., Bietti, M., & Leonori, D. Practical and Selective sp C–H Bond Chlorination via Aminium Radicals. Citing this paper Please note that where the full-text provided on Manchester Research Explorer is the Author Accepted Manuscript or Proof version this may differ from the final Published version. It is advised that you check and use the publisher's definitive version. General rights Copyright and moral rights for the publications made accessible in the Research Explorer are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights
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