Ketones isoprenylation

Since Lewis base additives and basic solvents such as tetrahydrofuran are known to deaggregate polymeric organolithium compounds, (21,23,26) it was postulated that ketone formation would be minimized in the presence of sufficient tetrahydrofuran to effect dissociation of the aggregates. In complete accord with these predictions, it was found that the carbonation of poly(styryl)lithium (eq. 9), poly(isoprenyl)-lithium, and poly(styrene-b-isoprenyl)lithium in a 75/25 mixture (by volume) of benzene and tetrahydrofuran occurs quantitatively to produce the carboxylic acid chain ends (8 ). 

The activated zinc obtained by electrochemical reduction of Zn2+ in dimethylformamide has been used for the isoprenylation of aldehydes and ketones. This has been reported by Tokuda and coworkers (equation 4)10. 

The isoprenylation of isovaleraldehyde led to the product in 68% isolated yield, higher than with a conventional procedure using zinc dust in DMF, or refluxing THF. The same procedure was used for the coupling reaction of allylic bromides with aldehydes and ketones, via the preliminary formation of organozinc compounds coming from the reaction between the electrolytic zinc and allylic bromides12. 

FTiR (wavenumber-assignment) cm V- C=0 1690 (carboxyl), 1720 (aldehyde), 1745 (ketone) 855 -frans-isoprenyl unit ... 

Ziegler polymerization of, 45,46 1,3-Divinyldisiloxane, polymers with 1,1 -bis(dimethyl-l-isoprenyl silyl) ferrocene, 118 Divinyl ketones,... 

Reaction of [2- " C]acetone with vinylmagnesium bromide (Figure 6.75, Procedure A) provided 2-methyl-3-[2- " C]buten-2-ol (257), which upon treatment with PBra rearranged to give 3,3-dimethyl[3- " C]allyl bromide (258). The latter was used for the alkylation of ethyl acetoacetate, thereby extending the carbon skeleton of the /3-keto ester by a labeled five-carbon (isoprenyl) unit. The initially formed alkylated intermediate 259 was not isolated but immediately saponified and decarboxylated to give ketone 260. Subsequent Homer-Wadsworth-Emmons olefination and reduction of the separated trans-ester 261 converted 260 into [T- Clgeraniol 12621. 

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