Highly Stereoselective Synthesis of 2-Amino-3-C-methyl-2,3-dideoxyaldoses by C₃-Chain Elongation via Homoaldol Reaction of Sugar Aldehydes

Abstract

A flexible strategy for the stereoselective synthesis of branched amino sugar analogues is described. It is based on a C₃-chain elongation of suitable protected aldoses. By using the sequence homoaldol reaction, epoxidation, and methanolysis α-methyl allo-furanosides are obtained. Proximate amination of the corresponding triflates afford the title compounds. All reactions proceed with high yield, high diastereoselectivities, and allow for a broad application.

Key words

homoaldol reaction - stereoselective synthesis - furanosides - aminoaldoses - carbamates

References

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1

X-ray crystal structure analysis.

7

A research in Scifinder afforded no hit.

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X-ray crystal structure analysis of 7c: Formula C₁₇H₂₈O₈, M = 360.39, colorless crystal 0.30 × 0.20 × 0.10 mm, a = 10.0328(3), b = 9.4646(3), c = 10.1594(3) Å, β = 106.772(2)˚, V = 923.66(5) Å^³, ρ_calc = 1.296 g cm^-³, µ = 0.861 mm^-¹, empirical absorption correction (0.782 ≤ T ≤ 0.919), Z = 2, monoclinic, space group P2₁ (No. 4), λ = 1.54178 Å, T = 223 K, ω and φ scans, 5102 reflections collected ± h, ± k, ± l), [(sin θ)/λ] = 0.60 Å^-¹, 2615 independent (R _int = 0.030) and 2563 observed reflections [I ≥ 2 σ (I)], 233 refined parameters, R = 0.034, wR ^² = 0.089, Flack parameter -0.10 (19), max. residual electron density 0.14 (-0.18) e Å^-³, hydrogen atoms calculated and refined as riding atoms.

17

Data set was collected with a Nonius KappaCCD diffractometer. Programs used: data collection COLLECT,^¹8 data reduction Denzo-SMN,^¹9 absorption correction Denzo,^²0 structure solution SHELXS-97,^²¹ structure refinement SHELXL-97,^²² and graphics Mopict.^²³

24

CCDC 747428 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: [phone], E-mail: [e-mail]].