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Application of the Brook Rearrangement in Tandem with Single Electron Transfer Oxidative and Radical Processes
Author(s) -
Klychnikov Mikhail K.,
Pohl Radek,
Císařová Ivana,
Jahn Ullrich
Publication year - 2020
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.202000126
Subject(s) - chemistry , cyclopentane , radical cyclization , tandem , stereocenter , nucleophile , cascade reaction , cyclopentanes , radical ion , acylation , electrophile , stereochemistry , medicinal chemistry , photochemistry , organic chemistry , enantioselective synthesis , catalysis , ion , materials science , composite material
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 α,γ‐dioxygenated ε,ζ‐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 β‐dicarbonyl enolates, which were also transformed to cyclopentane and cyclohexane derivatives under oxidative conditions.