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

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F20%3A00523805" target="_blank" >RIV/61388963:_____/20:00523805 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/00216208:11310/20:10420980

Výsledek na webu

<a href="https://chemistry-europe.onlinelibrary.wiley.com/doi/abs/10.1002/ejoc.202000126" target="_blank" >https://chemistry-europe.onlinelibrary.wiley.com/doi/abs/10.1002/ejoc.202000126</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/ejoc.202000126" target="_blank" >10.1002/ejoc.202000126</a>

Jazyk výsledku

angličtina

Název v původním jazyce

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

Popis výsledku v původním jazyce

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.

Název v anglickém jazyce

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

Popis výsledku anglicky

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.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10401 - Organic chemistry

Projekt

<a href="/cs/project/GA16-18513S" target="_blank" >GA16-18513S: Tandemové sigmatropní přesmyky/radikálové reakce - nové produktivní spojení v organické chemii</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2020

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

European Journal of Organic Chemistry

ISSN

1434-193X

e-ISSN

—

Svazek periodika

2020

Číslo periodika v rámci svazku

19

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

13

Strana od-do

2854-2866

Kód UT WoS článku

000522270900001

EID výsledku v databázi Scopus

2-s2.0-85082538582