某些 1-C-受体取代的糖醛在叠氮羟化条件下的行为。

Behaviour of some 1-C-acceptor-substituted glycals under azidohydroxylation conditions.

机构信息

Department of Organic Chemistry, University of Debrecen, PO Box 400, H-4002, Debrecen, Hungary; University of Debrecen, Doctoral School of Chemistry, PO Box 400, H-4002, Debrecen, Hungary.

Department of Organic Chemistry, University of Debrecen, PO Box 400, H-4002, Debrecen, Hungary.

出版信息

Carbohydr Res. 2023 Jul;529:108825. doi: 10.1016/j.carres.2023.108825. Epub 2023 Apr 27.

DOI:10.1016/j.carres.2023.108825

PMID:37253301

Abstract

Azidohydroxylation of 1-carbamoyl, 1-methoxycarbonyl and 1-cyano substituted d-lyxo and d-arabino configured O-peracylated glycals was studied and the reaction conditions were optimized. Under these conditions (3 equiv. NaN/2 equiv. PIFA/0.3 equiv. TEMPO/50 equiv. HO/dry DCM/0 °C/Ar) the expected 3-azido-3-deoxy ulopyranosonic acid derivatives were isolated in good yield with α-d-galacto configuration exclusively from the reaction of the 1-carbamoyl and 1-methoxycarbonyl substituted d-lyxo configured O-peracetylated glycals, while the transformation of the 1-cyano derivative gave a 2,3-vicinal diazide in low yield. The 1-carbamoyl d-arabino configured O-perbenzoylated glycal gave a mixture of α-d-gluco and α-d-manno configured azidohydroxylated products with d-gluco preference. The analogous 1-methoxycarbonyl derivative gave an inseparable product mixture and no transformation was detected with the respective 1-cyano glycal.

摘要

1-氨甲酰基、1-甲氧羰基和 1-氰基取代的 d-赤藓糖和 d-阿拉伯糖构型的 O-过酰化糖醛的叠氮羟化反应进行了研究，并优化了反应条件。在这些条件下（3 当量 NaN/2 当量 PIFA/0.3 当量 TEMPO/50 当量 HO/干燥 DCM/0°C/Ar），预期的 3-叠氮基-3-脱氧吡喃糖酸衍生物以良好的产率分离出来，并且仅从 1-氨甲酰基和 1-甲氧羰基取代的 d-赤藓糖构型的 O-过乙酰化糖醛的反应中得到 α-d-半乳糖构型，而 1-氰基衍生物的转化则以低产率得到 2,3-顺式二氮杂。1-氨甲酰基 d-阿拉伯糖构型的 O-苯甲酰化糖醛得到α-d-吡喃葡萄糖和α-d-吡喃甘露糖构型的叠氮羟化产物的混合物，具有 d-吡喃葡萄糖的偏好。类似的 1-甲氧羰基衍生物得到了不可分离的产物混合物，并且相应的 1-氰基糖醛没有发生转化。