Formal Synthesis of 3-Deoxy-d-manno-Octulosonic Acid (KDO) and 3-Deoxy-d-arabino-2-heptulosonic Acid (DAH)

Abstract

Practical synthetic routes to 3-deoxy-d-manno-octulo­sonic acid (KDO) and 3-deoxy-d-arabino-2-heptulosonic acid (DAH) from common sugar substrates are reported. Chain homologation of the sugar substrates was accomplished by Wittig olefination and Corey–Fuchs alkynylation. A new cyclization strategy was investigated to access the desired pyranosyl isomer of the KDO target.

Key words

carbohydrates - Wittig - Corey–Fuchs - cyclization

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• 20 Analytical data of 14: [α]_D ³³ +25.94 (c 0.175, CHCl₃); ¹H NMR (400 MHz, CDCl₃): δ = 7.45–7.12 (m, 15 H), 4.91 (d, J = 10.6 Hz, 1 H), 4.65 (dd, J = 17.3, 11.6 Hz, 2 H), 4.59 (d, J = 12.2 Hz, 1 H), 4.57 (d, J = 10.6 Hz, 1 H), 4.51 (d, J = 12.2 Hz, 1 H), 4.04 (m, 1 H), 3.83 (s, 3 H), 3.82–3.57 (m, 4 H), 2.30 (dd, J = 12.6, 5.0 Hz, 1 H), 2.09 (t, J = 12.6 Hz, 1 H); ¹³C NMR (100 MHz, CDCl₃): δ = 170.3, 138.4, 138.3, 138.2, 128.4, 128.3, 127.9, 127.8, 127.6, 127.6, 127.5, 94.9, 78.0, 77.5, 74.9, 73.3, 73.1, 71.8, 68.9, 53.3, 36.1; HRMS (ESI): m/z [M + Na]⁺ calcd for C₂₉H₃₂O₇Na: 515.2030; found: 515.2040