Abstract
The asymmetric synthesis of 1,3-dihydroxy-2-ketones bearing two quaternary stereocenters in α- and α′-position starting from 2,2-dimethyl-1,3-dioxan-5-one-SAMP-hydrazone is described. The protocol involves four consecutive α/α′-alkylations, the last one being carried out in the presence of DMPU as additive. After acidic cleavage of both the chiral auxiliary and the acetal function in a two-phase system, the title compounds are obtained with high stereoselectivity (de ≥ 91-97%, ee ≥ 96%) and in moderate to very good overall yields (14-61%). In addition, 1,2-quaternary 1,3-protected 1,2,3-triols were obtained by nucleophilic 1,2-addition to the carbonyl group as single stereoisomeres (de, ee ≥ 96%) in excellent yields.
Key words
asymmetric synthesis - quaternary stereocenters - α-alkylation - SAMP/RAMP-hydrazones - 1,2-addition
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