Lithium reagents, anomeric

Tetrahedral anomeric lithium reagents are [10], initially restricted to the 2-deoxy sugar series in order to avoid the facile -elimination of the substituent at position 2, is usable if a protective metallation at the C2-substituent is carried out before the metallation event at Cl by reductive lithiation or transmetallation of the corresponding stannanes [10]. This process has... 

A new phosphorylating reagent, dibenzyl phosphorofluoridate, has been introduced. In the presence of caesium fluoride as base it reacts with primary and anomeric hydroxy groups preferentially. Secondary hydroxy groups, e.q.. those of partially protected myo-inositol, can be phosphorylated after deprotection with butyl lithium. 1,2-Di-phosphates were obtained in good to excellent yields by treatment of vicinal diols with diethyl phosphorochloridate and butyl lithium there was no evidence of formation of cyclic phosphates, the predominant products when other bases are used. Q-Glycosylation of phosphonic and phosphinic acids has been achieved by the trichloroacetimidate method examples are given in Scheme 4. ... 

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