Application of the Brook Rearrangement in Tandem with Single Electron Transfer Oxidative and Radical Processes

0523805 - ÚOCHB 2021 RIV DE eng J - Článek v odborném periodiku
Klychnikov, Mikhail - Pohl, Radek - Císařová, I. - Jahn, Ullrich
Application of the Brook Rearrangement in Tandem with Single Electron Transfer Oxidative and Radical Processes.
European Journal of Organic Chemistry. Roč. 2020, č. 19 (2020), s. 2854-2866. ISSN 1434-193X. E-ISSN 1099-0690
Grant CEP: GA ČR(CZ) GA16-18513S
Institucionální podpora: RVO:61388963
Klíčová slova: Brook rearrangement * radical reactions * electron transfer * cyclization * tandem reactions
Obor OECD: Organic chemistry
Impakt faktor: 3.021, rok: 2020
Způsob publikování: Omezený přístup
https://chemistry-europe.onlinelibrary.wiley.com/doi/abs/10.1002/ejoc.202000126

Merging rearrangement with radical reactions is a largely unexplored field but may hold promise for approaching scaffolds that are inaccessible by other methodology. Here a tandem nucleophilic substitution/Brook rearrangement/single-electron transfer oxidation/radical oxygenation strategy is presented, through which alpha,gamma-dioxygenated epsilon,zeta-unsaturated amides are efficiently prepared in a single step from enantiomerically enriched allylepoxides and 2-silylacetamides. The resulting compounds can be easily transformed by persistent radical effect-based 5-exo-trig or 6-endo-trig radical cyclization reactions to functionalized carbocycles bearing three or four stereocenters. The stereochemical outcome of the cyclization reactions can predicted by the Beckwith-Houk model. The cyclic compounds can be easily diversified by post-cyclization modifications. The tandem process can be further extended by an acylation step leading to beta-dicarbonyl enolates, which were also transformed to cyclopentane and cyclohexane derivatives under oxidative conditions.
Trvalý link: http://hdl.handle.net/11104/0308098