Notizen: Influence of Counter Ion Structure on the Direction of the Phase Transfer Catalytic Methylation of an Enol [1]

Abstract
Phase transfer catalytic (PTC) methylations of deoxybenzoin by dimethyl sulfate can be steered towards enol ether formation by large, sterically shielded ammonium ions or – more strongly – by large highly delocalized phospho-iminium (and presumably other large) cations. The C-alkylation direction is favoured by small, hard ammonium ions of the type RNMe3 + and by crown ethers, particularly benzo-crowns. O/C ratios can be varied between 0,75 and 63, the largest effects so far reported for ambident anions. These results should give guide-lines for alkylations of other ambident ions.

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