Dialdehydes, cyclization with nitroalkanes

Aldol-type cyclization of dialdehydes with nitroalkanes is a valuatde syndietic loute to amino sugars, amino cyclitols and nucleosides of amino sugars. Recently, die cyclization of die di- and tetra- de-hydes derived from sucrose (15) with nitroalkanes has appeared. It is notewordiy that the oxidadve cleavage of sucrose with LTA affords the dialdehyde selectively (Scheme 8). ... 

The dialdehydes from periodate oxidation of methyl 4,6-0-benzylidene-a-and -p-D-glucopyranoside reacted with appropriate Wittig reagents to give such dienes as (400) that afforded cyclized products [e.g. (401)] with nitromethane by a double Michael condensation, whereas only one of the olefinic linkages was attacked, without cyclization, with ethyl cyanoacetate and malononitrile. Details of the reactions of these dialdehydes with nitroalkanes (see Vol. 8, p. 108), ethyl cyanoacetate (see VoL 8, p. IlOX and other carbanions to give various branched-chain heptoseptanosides have also been reported. ... 

C-l, obviously owing to base-catalyzed epimerization at the aldehyde stage. As compared with nitromethane cyclizations (wherein such epi-merizations have not been observed), nitroalkanes react less readily, thus providing longer exposure of the dialdehyde to the alkaline conditions required for cyclization. 

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