Derivatives (chloro, bromo, pentafluorobenzoate, mesylate, phosphate) of a-hydroxy-(Z)-�,?-ethylenic esters (1) undergo in selective allylic substitution with rearrangement of double bond, SN2', rather than SN2 substitution. For this study it was possible to get the alkylation and arylation of 1 in ?-position with different substituents, R= n-Bu, t-Bu, Me, sec-Bu, CH3CH2NBoc, Ph, biphenyl and anisole in 60-95% yield using RCuCNLi and R2CuLi (Gilman) cuprates to yield ?-R-a,�-unsaturated esters. The scope and limitations of the current efforts to expand the ?-alkylation or arylation protocol with more substituents (heterocycles) is described.

γ-Alkylation and γ-arylation of α-derivatives-(<i>Z</i>)-β,γ-ethylenic esters through S<sub>N</sub>2' substitution using Gilman and cyanocuprates

245th National Meeting (2013)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.

γ-Alkylation and γ-arylation of α-derivatives-(Z)-β,γ-ethylenic esters through SN2' substitution using Gilman and cyanocuprates

γ-Alkylation and γ-arylation of α-derivatives-(Z)-β,γ-ethylenic esters through S_N2' substitution using Gilman and cyanocuprates