Achmatowicz O, Bielski R
Carbohydr Res. 1977 May;55:165-76. doi: 10.1016/s0008-6215(00)84452-3.
Methyl alpha-L- and alpha-D-glucopyranosides have been synthesized from methyl (R)- and (S)-(2-furyl)glycolates (3), respectively. The key intermediates, methyl 6-O-benzyl-2,3-dideoxy-L(and D)-hex-2-enopyranosid-4-uloses (13), were obtained in seven steps from the ester 3, without change of configuration of the asymmetric center, which became C-5 in the sugar molecule. Reduction of the ketone group at C-4 in the glycoside 13 with sodium borohydride afforded the corresponding methyl 6-O-benzyl-2,3-dideoxy-erythro-hex-2-enopyranosides (14). Epoxidation of the double bond in 14, followed by oxirane ring-opening in the anhydro sugar 16, and subsequent catalytic hydrogenolysis of the benzyl group led to the title compounds.
α-L-和α-D-吡喃葡萄糖苷甲酯分别由(R)-和(S)-(2-呋喃基)乙醇酸甲酯(3)合成。关键中间体6-O-苄基-2,3-二脱氧-L(和D)-己-2-烯吡喃糖-4-ulose(13)可由酯3经七步反应制得，不对称中心的构型不变，该不对称中心在糖分子中成为C-5。用硼氢化钠还原糖苷13中C-4位的酮基，得到相应的6-O-苄基-2,3-二脱氧-赤藓糖基己-2-烯吡喃糖苷(14)。14中的双键环氧化，随后脱水糖16中的环氧乙烷开环，以及苄基的后续催化氢解，得到标题化合物。
