Lithium homoenolates, functionalized

Eunctionalized organolithium compounds, having a protected carboxylic acid functionality, can also be considered as masked lithium tris-homoenolates and were prepared by DTBB-catalyzed (5%) Uthiation of the corresponding )-chlorinated materials. Eor instance, compound 227 in THE at —78°C leads to the expected organoUthium intermediate 228, which reacts with a series of electrophiles present in the reaction medium... 

In the presence of a Lewis acid, alkyl 2-silyloxycyclopropanecarboxylates (14) react with a wide range of carbonyl compounds to give a diester (15), which has b n converted to a variety of furan derivatives (Scheme 18). An interesting use of the oxyanionic tautomer of a homoenolate involves the reaction of a magnesium cyclopropanolate (12) with the lithium enolate of cyclohexanone, from which a tricyclic ring containing a functionalized cycloheptanone (13) is formed in a single step (Scheme 18). ... 

Functionalized allyllithium compounds of type XIII are also homoenolate equivalents [122,130], but in their reaction with electrophiles sometimes it is not possible to control the regioselectivity. These compounds have been prepared mainly by either deprotonation or tin-lithium exchange. Deprotonation of (F)-cinnamyl-N,N-diisopropylcarbamate 155 with n-BuLi in the presence of (-[-sparteine in toluene gave a configurationally stable lithiated O-allyl carbamate (epi-156), which equilibrates at -50 °C to give the (R)-intermediate 156. Whereas the reaction of these compounds with Mel and MeOTs gave the /-attack, however acylation, silylation and stannylation took place at the a-position (Scheme 2.21) [131]. 

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