Indium-Mediated Allenylation of Aldehydes and Its Application in Carbohydrate Chemistry: Efficient Synthesis of D-Ribulose and 1-Deoxy-D-ribulose

A two-step reaction sequence starting with the indium-mediated allenylation of aldehydes with 4-bromo-2-butyn-1-ols and subsequent ozonolysis of the resulting allenylic product was developed to generate a variety of dihydroxyacetone derivatives. The regioselectivity of the indium-promoted C-C bond-forming reaction can be manipulated through hydroxy protecting groups on 4-bromo-2-butyn-1-ol, yielding either allenes or alkynes as preferred products. Compared to established protocols, the necessary amount of indium for this type of allenylation can be decreased by a factor of two to four. The versatility of this strategy was demonstrated in the stereoselective and straightforward synthesis of D-ribulose and 1-deoxy-D-ribulose.