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

Result code in 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>
Result on the web
<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>

Result language
angličtina
Original language name
Elucidation of the Reaction Mechanism of ortho ->alpha Transmetalation Reactions of Alkyl Aryl Sulfone Carbanions
Original language description
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
Czech name
—
Czech description
—

Type
J<sub>x</sub> - Unclassified - Peer-reviewed scientific article (Jimp, Jsc and Jost)
CEP classification
CC - Organic chemistry
OECD FORD branch
—

Project
<a href="/en/project/GAP207%2F11%2F1598" target="_blank" >GAP207/11/1598: A New Carbanion Rearrangement and Its Application in Organic Synthesis</a><br>
Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year
2014
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Similar results(10)