Direct conversion of 1-deoxy-1-nitroalditols to methyl glycofuranosides

作者：Vojtech M; Petrusova M; Pribulova B; Petrus L^*

来源：Tetrahedron Letters, 2008, 49(19): 3112-3116.

DOI：10.1016/j.tetlet.2008.03.044

• Nef reaction
• stereoselectivity
• 1-deoxy-4-nitroalditol
• nitronate
• ring-closure reaction
• intramolecular nucleophilic addition
• walden inversion
• methyl glycofuranoside

Treatment of the sodium nitronate forms of 1-deoxy-1-nitrohexitols with methanolic sulfuric or hydrochloric acid at - 30 degrees C leads to their regiospecific conversion to the corresponding methyl glycofuranosides. The reaction exhibits more pronounced stereoselectivity for 1-deoxy-1-nitroalditols with the 2,3-erythro configuration than with the 2,3-threo substrates and cis methyl glycofuranosides are the major products. The observed stereo selectivity indicates the lysis of the protonated aci-nitro form which is a two-step process consisting of nucleophilic addition to the protonated carbon-nitrogen double bond followed by the bimolecular nucleophilic substitution of the nitrogen-containing residue.

• 出版日期2008-5-5