2-azido-3,4,6-tri-O-benzyl-2-deoxy-D-glucono-1,5-lactone | 175981-90-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 2-azido-3,4,6-tri-O-benzyl-2-deoxy-D-glucono-1,5-lactone
• 英文别名: (3R,4R,5S,6R)-3-azido-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-2-one
• CAS: 175981-90-5
• 化学式: C₂₇H₂₇N₃O₅
• 分子量: 473.528
• InChiKey: JZVINQNAXZEQKZ-VEYUFSJPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  35
• 可旋转键数：
  11
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  68.4
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  2-azido-3,4,6-tri-O-benzyl-2-deoxy-D-glucono-1,5-lactone 在 三乙基硅烷 、 sodium hydroxide 、 正丁基锂 、 cerium(III) chloride 、 三氟化硼乙醚 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 二氯甲烷 、 乙腈 为溶剂， 反应 4.0h， 生成 3,7-anhydro-4-azido-5,6,8-tri-O-benzyl-1,2,4-trideoxy-D-glycero-D-gulo-oct-1-ynitol
  参考文献：
  名称：

  Synthesis of α- and β-Glycosyl Asparagine Ethylene Isosteres (C-Glycosyl Asparagines) via Sugar Acetylenes and Garner Aldehyde Coupling

  摘要：

  A convergent approach has been developed for the synthesis of C-glycosyl amino acids in which the glycinyl moiety CH(NH2)CO2H is connected to the anomeric center of the sugar residue by a three carbon atom tether. Essentially, these compounds are isosteres of N-glycosyl asparagines in which the amide group has been replaced by an ethylene bridge. Following the coupling of alpha- or beta-D-linked lithium C-glycoside acetylides with N-Boc D-serinal acetonide (Garner aldehyde), the resulting adducts were transformed into the final N-Boc-C-glycosyl-alpha-aminopentanoic acids via reduction of the triple bond, deoxygenation, and oxidative cleavage of the oxazolidine ring. By this protocol, 12 C-glycosyl asparagines, six pairs of alpha- and beta-anomers, have been prepared incorporating the gluco, galacto, manno, and the corresponding 2-acetamido-2-deoxy residues.

  DOI：

  10.1021/jo020054m
• 作为产物：
  描述：

  2-azido-3,4,6-tri-O-benzyl-2-deoxy-D-glucopyranose 在 pyridinium chlorochromate 作用下， 生成 2-azido-3,4,6-tri-O-benzyl-2-deoxy-D-glucono-1,5-lactone
  参考文献：
  名称：

  Synthesis of α- and β-Glycosyl Asparagine Ethylene Isosteres (C-Glycosyl Asparagines) via Sugar Acetylenes and Garner Aldehyde Coupling

  摘要：

  A convergent approach has been developed for the synthesis of C-glycosyl amino acids in which the glycinyl moiety CH(NH2)CO2H is connected to the anomeric center of the sugar residue by a three carbon atom tether. Essentially, these compounds are isosteres of N-glycosyl asparagines in which the amide group has been replaced by an ethylene bridge. Following the coupling of alpha- or beta-D-linked lithium C-glycoside acetylides with N-Boc D-serinal acetonide (Garner aldehyde), the resulting adducts were transformed into the final N-Boc-C-glycosyl-alpha-aminopentanoic acids via reduction of the triple bond, deoxygenation, and oxidative cleavage of the oxazolidine ring. By this protocol, 12 C-glycosyl asparagines, six pairs of alpha- and beta-anomers, have been prepared incorporating the gluco, galacto, manno, and the corresponding 2-acetamido-2-deoxy residues.

  DOI：

  10.1021/jo020054m

文献信息

• Expeditious Synthesis of β-Linked Glycosyl Serine Methylene Isosteres (β-C-Gly Ser) via Ethynylation of Sugar Lactones
  作者：Alessandro Dondoni、Giandomenico Mariotti、Alberto Marra、Alessandro Massi

  DOI：10.1055/s-2001-18058

  日期：——

  The addition of the lithium derivative of N-Boc 4-ethynyl-2,2-dimethyl-1,3-oxazolidine to tetra-O-benzyl-d-gluco- and galactonolactone and 2-azido-2-deoxy congeners afforded the corresponding ethynyl ketoses in fairly good yields (64-78%). Following the conversion of the ketoses into O-acetates and removal of the acetoxy group by silane reduction, the resulting β-linked ethynyl glycosides were transformed into N-Boc C-glycosyl α-aminobutyric acids by reduction of the triple bond using H2/Pd(OH)2 and oxidative cleavage of the oxazolidine ring using the Jones’ reagent. After the removal of O-benzyl groups of the carbohydrate moieties by hydrogenation and the reduction of azido to amino group, all compounds were subjected to acetylation and isolated as O- and N-acetyl derivatives. The C-glycosyl α-amino acids prepared correspond to methylene isosteres of O-glycosyl serines.

  将N-Boc 4-乙炔基-2,2-二甲基-1,3-噁唑烷的锂衍生物与四-O-苄基-d-葡萄糖和d-半乳糖内酯以及2-叠氮-2-脱氧同系物反应，得到相应的乙炔基酮，产率相当不错（64-78%）。在将酮转化为O-醋酸酯并通过硅烷还原去除醋酸氧基后，得到的β-连接乙炔基糖苷通过使用H2/Pd(OH)2还原三重键和利用琼斯试剂氧化开环将噁唑烷环转化为N-Boc C-糖苷 α-氨基丁酸。在通过氢化去除糖部分的O-苄基后，并将叠氮基还原为氨基后，所有化合物均经过醋酸化处理，并以O-和N-醋酸衍生物的形式分离出来。所制备的C-糖苷 α-氨基酸对应于O-糖苷丝氨酸的亚甲基等构体。
• Alkylidenation of Sugar Lactones and Further Transformation to<i>C</i>-Glycosides
  作者：Juan Xie、Adeline Molina、Stanislas Czernecki

  DOI：10.1080/07328309908544013

  日期：1999.1

  The Wittig reaction of (carbethoxymethylene)triphenylphosphorane with perbenzylated sugar delta-lactones and their 2-acetamido-2-deoxy derivatives is described. It is shown that this olefination occurred readily with the galacto and gluco derivatives, leading stereoselectively to Z-C-glycosylidenes in good yields. However, the same reaction with the perbenzylated 2-deoxy-D-arabino-hexono-1,5-lactone and the mannonolactones worked poorly. Reduction over Pd/C followed by acetylation of the obtained C-glycosylidenes led stereoselectively to peracetylated beta-C-glycosides and amino beta-C-glycosides. The olefin function could also be reduced selectively by Raney nickel or NiCl2/NaBH4, affording the perbenzylated C-glycosides and amino beta-C-glycosides. Other transformation of the enol ether function is also reported.
• Addition of trialkylaluminum reagents to glyconolactones. Synthesis of 1-C-methyl GlcNAc oxazoline and thiazoline
  作者：Spencer Knapp、Chunhua Yang、Thomas Haimowitz

  DOI：10.1016/s0040-4039(02)01506-x

  日期：2002.9

  Addition of carbon nucleophiles to 2-acetamido-2-deoxygluconolactones fails for many reagents, but trialkylaluminums add alkyl smoothly. The product of Methyl addition to 2-acetamido-2-deoxy-D-gluconolactone has been converted to 1-C-methyl GlcNAc thiazoline, a potential N-acetylhexosaminidase inhibitor, and to an O-protected I-C-Me GlcNAc oxazoline, a potential I-C-Me GlcNAc donor. (C) 2002 Elsevier Science Ltd. All rights reserved.
• Convenient Preparation of Perbenzylated 2-Azido and 2-<i>N</i>-Acetylamino-2-Deoxy-<scp>d</scp>-Hexono-1,5-Lactones by Oxidation of the Corresponding Lactols
  作者：Ebtissam Ayadi、Stanislas Czernecki、Juan Xie

  DOI：10.1080/07328309608005438

  日期：1996.2

  2-Azido-3,4,6-tri-O-benzyl-2-deoxy-D-galacto, gluco and mannopyranoses (1, 2, 3) were oxidized with DMSO in the presence of acetic anhydride. From 1 and 2 the corresponding lactone derivatives were obtained in good yield (89-92%), whereas from 3, glucono-1,5-lactone was obtained (92%) after complete epimerization at C-2. 2-N-Acetylamino-3,4,6-tri-O-benzyl-2-deoxy-D-galacto, gluco and mannopyranoses (7, 8, 9) were obtained from the corresponding 2-azido phenylselenoglycopyranosides (13, 14, 15) by reduction, N-acetylation and hydrolysis catalyzed by mercury trifluoroacetate. Oxidation of 7 and 8 by tetra-n-propylammonium tetra-oxoruthenate (VII) in the presence of 4-methylmorpholine-N-oxide afforded the corresponding lactones in good yield (90%) and high purity. Epimerization at C-2 occurred during oxidation of 9 and perbenzylated D-glucono-1,5-lactone (11) was obtained (90%).
• Stereocontrolled synthesis of 2-azido and 2-N-acetylamino-2-deoxy-β-<scp>D</scp>-C-glycosides from the corresponding lactones
  作者：Ebtissam Ayadi、Stanislas Czernecki、Juan Xie

  DOI：10.1039/cc9960000347

  日期：——

  The reaction of perbenzylated 2-azido-2-deoxy-D-hexono-1,5-lactones with organometallic reagents followed by reduction provides a new stereocontrolled synthesis of 2-azido-2-deoxy-beta-D-C-glycosides, which can be efficiently transformed into 2-N-acetylamino-2-deoxy-beta-D-C-glycosides.