Reaction of glycals with trifluoroacetic anhydride and ammonium nitrate. A novel cleavage reaction of glycals.

After aq. workup (pH>7) of the title reaction mixt., 3,4,6-tri-O-acetyl-D-glucal, 3,4,6-tri-O-acetyl-D-galactal and 3,4-di-O-acetyl-L-rhamnal yielded the following ring cleavage products: (E)-(3R),5-diacetoxy-(4R)-formyloxy-1-nitro-1-pentene (I), (E)-(3S),5-diacetoxy-(4R)-formyloxy-1-nitro-1-pentene...

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Journal Title: Journal of Organic Chemistry Vol. 51; no. 13; pp. 2617 - 2618
Authors: Pimchit Dampawan, Walter W. Zajac, Dolores Ditrow
Format: Article
Published: 1986
Application Date: Dep. Chem.,Villanova Univ.,Villanova,PA,USA.
Subjects:
Summary: After aq. workup (pH>7) of the title reaction mixt., 3,4,6-tri-O-acetyl-D-glucal, 3,4,6-tri-O-acetyl-D-galactal and 3,4-di-O-acetyl-L-rhamnal yielded the following ring cleavage products: (E)-(3R),5-diacetoxy-(4R)-formyloxy-1-nitro-1-pentene (I), (E)-(3S),5-diacetoxy-(4R)-formyloxy-1-nitro-1-pentene and (E)-(3S)-acetoxy--(4S)-formyloxy-1-nitro-1-pentene in 90, 85 and 93% yields, resp. 4,6-Di-O-acetyl-3-O-methyl-D-glucal and 3,4,6-tri-O-acetyl-D-allal gave only a 40% yield of I. 1H NMR confirmed that the cleavage products result from a Grob type fragmentation of the initially formed 1-O-trifluoroacetyl-2-deoxy-2-nitropyranoses.
ISSN: 0022-3263