Elucidation of the Reaction Mechanism of ortho ->alpha Transmetalation Reactions of Alkyl Aryl Sulfone Carbanions

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F14%3A00430905" target="_blank" >RIV/61388963:_____/14:00430905 - isvavai.cz</a>

Výsledek na webu

<a href="http://dx.doi.org/10.1002/ejoc.201402171" target="_blank" >http://dx.doi.org/10.1002/ejoc.201402171</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/ejoc.201402171" target="_blank" >10.1002/ejoc.201402171</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Elucidation of the Reaction Mechanism of ortho ->alpha Transmetalation Reactions of Alkyl Aryl Sulfone Carbanions

Popis výsledku v původním jazyce

The sulfonyl group, as an electron-accepting function, displays a strong acidifying effect on neighboring alpha-hydrogen atoms, leading to their deprotonation by bases. Recently, reversal of the metalation selectivity of alpha,gamma-branched alkyl aryl sulfones was described, which instead undergo directed ortho-metalation with good regioselectivity, despite having a more acidic alpha-proton. Upon warming, a transmetalation to the alpha-carbanion proceeds; however, nothing is known about the course of this transmetalation. Here, a mechanistic study is presented that sheds light on the facility of the initial met-alation and the subsequent transmetalation. Large kinetic isotope effects were observed for both the initial deprotonation and the ortho ->alpha transmetalation, which strongly influence the initial metalation selectivity. The results of a kinetic investigation of the transmetalation and a crossover study indicate that a concerted intermolecular pathway, either from an aggregat

Název v anglickém jazyce

Elucidation of the Reaction Mechanism of ortho ->alpha Transmetalation Reactions of Alkyl Aryl Sulfone Carbanions

Popis výsledku anglicky

The sulfonyl group, as an electron-accepting function, displays a strong acidifying effect on neighboring alpha-hydrogen atoms, leading to their deprotonation by bases. Recently, reversal of the metalation selectivity of alpha,gamma-branched alkyl aryl sulfones was described, which instead undergo directed ortho-metalation with good regioselectivity, despite having a more acidic alpha-proton. Upon warming, a transmetalation to the alpha-carbanion proceeds; however, nothing is known about the course of this transmetalation. Here, a mechanistic study is presented that sheds light on the facility of the initial met-alation and the subsequent transmetalation. Large kinetic isotope effects were observed for both the initial deprotonation and the ortho ->alpha transmetalation, which strongly influence the initial metalation selectivity. The results of a kinetic investigation of the transmetalation and a crossover study indicate that a concerted intermolecular pathway, either from an aggregat

Druh

J_x - Nezařazeno - Článek v odborném periodiku (Jimp, Jsc a Jost)

CEP obor

CC - Organická chemie

OECD FORD obor

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Projekt

<a href="/cs/project/GAP207%2F11%2F1598" target="_blank" >GAP207/11/1598: Nový karbaniontový přesmyk a jeho použití v organické syntéze</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2014

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

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Svazek periodika

2014

Číslo periodika v rámci svazku

21

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

14

Strana od-do

4610-4623

Kód UT WoS článku

000339493400021

EID výsledku v databázi Scopus

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