Sulfamides direct radical-mediated chlorination of aliphatic C-H bonds.
| Autor: | Short MA; Duke University, Department of Chemistry Box 90346 Durham North Carolina 27709-0354 USA j.roizen@duke.edu., Shehata MF; Duke University, Department of Chemistry Box 90346 Durham North Carolina 27709-0354 USA j.roizen@duke.edu., Sanders MA; Duke University, Department of Chemistry Box 90346 Durham North Carolina 27709-0354 USA j.roizen@duke.edu., Roizen JL; Duke University, Department of Chemistry Box 90346 Durham North Carolina 27709-0354 USA j.roizen@duke.edu. |
|---|---|
| Jazyk: | angličtina |
| Zdroj: | Chemical science [Chem Sci] 2019 Nov 08; Vol. 11 (1), pp. 217-223. Date of Electronic Publication: 2019 Nov 08. |
| DOI: | 10.1039/c9sc03428e |
| Abstrakt: | Given the prevalence of aliphatic amines in bioactive small molecules, amine derivatives are opportune as directing groups. Herein, sulfamides serve as amine surrogates to guide intermolecular chlorine-transfer at γ-C(sp 3 ) centers. This unusual position-selectivity arises because accessed sulfamidyl radical intermediates engage preferentially in otherwise rare 1,6-hydrogen-atom transfer (HAT) processes through seven-membered transition states. The site-selectivity of C-H abstraction can be modulated by adjusting the steric and electronic properties of the sulfamide nitrogen substituents, an ability that has not been demonstrated with other substrate classes. The disclosed reaction relies on a light-initiated radical chain-propagation mechanism to oxidize C(sp 3 )-H bonds efficiently. Competing Interests: There are no conflicts to declare. (This journal is © The Royal Society of Chemistry.) |
| Databáze: | MEDLINE |
| Externí odkaz: |
|