2,3,4-tri-O-benzyl-N-[(tert-butoxy)carbonyl]-5a-carba-2,5a-cyclo-α-D-glucopyranosylamine | 452081-59-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2,3,4-tri-O-benzyl-N-[(tert-butoxy)carbonyl]-5a-carba-2,5a-cyclo-α-D-glucopyranosylamine
• 英文别名: tert-butyl N-[(1S,2S,3R,4R,5R,6S)-4-(hydroxymethyl)-1,2,3-tris(phenylmethoxy)-6-bicyclo[3.1.0]hexanyl]carbamate
• CAS: 452081-59-3
• 化学式: C₃₃H₃₉NO₆
• 分子量: 545.676
• InChiKey: ZEXJGRADQPUZFZ-YRTTXNQMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  40
• 可旋转键数：
  13
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  86.2
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2,3,4-tri-O-benzyl-N-[(tert-butoxy)carbonyl]-5a-carba-2,5a-cyclo-α-D-glucopyranosylamine 在 palladium on activated charcoal 盐酸 、 氢气 作用下， 以 甲醇 、 水 为溶剂， 反应 23.0h， 以100%的产率得到5a-carba-2,5a-cyclo-α-D-glucopyranosylammonium chloride
  参考文献：
  名称：

  Conformationally Biased Mimics of Mannopyranosylamines: Inhibitors of β-Mannosidases?

  摘要：

  The enol ether 7 was prepared by cleavage of the N-O bond of the known isoxazolidine 3, followed by N-alkylation to 4, silylation and oxidation to the N-oxide 6, and Cope elimination. Cu-Catalysed cyclopropanation of 7 led to the diastereoisomeric cyclopropanes 8 and 9, which were subjected to a Curtius degradation, The resulting carbamates 12 and 16 were deprotected to the ammonium salts 14 and 18, respectively. Both salts adopt a B-1,B-4 conformation, similarly as the ester 8, while the isomeric ester 9 exists in a ca, 6:4 equilibrium of the C-4(1) and B-1,B-4 conformers. The beta-mannoside mimic 14 does not inhibit snail beta-mannosidase at 10 mM, but the alpha-mannoside mimic 18 inhibits Jack bean alpha-mannosidase (IC50 = 80 muM). These results are in keeping with the postulate that glycoside cleavage of beta-D-glycopyranosides requires a conformational change in agreement with the principle of stereoelectronic control.

  DOI：

  10.1002/1522-2675(200204)85:4<1118::aid-hlca1118>3.0.co;2-s
• 作为产物：
  描述：

  1L-(1,2,4/3,5)-3,4,5-tri-O-benzyl-2-(dimethylamino)-1-(hydroxymethyl)cyclopentane-3,4,5-triol 在 铜 咪唑 、 盐酸 、 四丁基氟化铵 、 一水合肼 、 间氯过氧苯甲酸 、 sodium nitrite 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 49.83h， 生成 2,3,4-tri-O-benzyl-N-[(tert-butoxy)carbonyl]-5a-carba-2,5a-cyclo-α-D-glucopyranosylamine
  参考文献：
  名称：

  Conformationally Biased Mimics of Mannopyranosylamines: Inhibitors of β-Mannosidases?

  摘要：

  The enol ether 7 was prepared by cleavage of the N-O bond of the known isoxazolidine 3, followed by N-alkylation to 4, silylation and oxidation to the N-oxide 6, and Cope elimination. Cu-Catalysed cyclopropanation of 7 led to the diastereoisomeric cyclopropanes 8 and 9, which were subjected to a Curtius degradation, The resulting carbamates 12 and 16 were deprotected to the ammonium salts 14 and 18, respectively. Both salts adopt a B-1,B-4 conformation, similarly as the ester 8, while the isomeric ester 9 exists in a ca, 6:4 equilibrium of the C-4(1) and B-1,B-4 conformers. The beta-mannoside mimic 14 does not inhibit snail beta-mannosidase at 10 mM, but the alpha-mannoside mimic 18 inhibits Jack bean alpha-mannosidase (IC50 = 80 muM). These results are in keeping with the postulate that glycoside cleavage of beta-D-glycopyranosides requires a conformational change in agreement with the principle of stereoelectronic control.

  DOI：

  10.1002/1522-2675(200204)85:4<1118::aid-hlca1118>3.0.co;2-s

文献信息

• Conformationally Biased Mimics of Mannopyranosylamines: Inhibitors of β-Mannosidases?
  作者：Lubos Remen、Andrea Vasella

  DOI：10.1002/1522-2675(200204)85:4<1118::aid-hlca1118>3.0.co;2-s

  日期：2002.4

  The enol ether 7 was prepared by cleavage of the N-O bond of the known isoxazolidine 3, followed by N-alkylation to 4, silylation and oxidation to the N-oxide 6, and Cope elimination. Cu-Catalysed cyclopropanation of 7 led to the diastereoisomeric cyclopropanes 8 and 9, which were subjected to a Curtius degradation, The resulting carbamates 12 and 16 were deprotected to the ammonium salts 14 and 18, respectively. Both salts adopt a B-1,B-4 conformation, similarly as the ester 8, while the isomeric ester 9 exists in a ca, 6:4 equilibrium of the C-4(1) and B-1,B-4 conformers. The beta-mannoside mimic 14 does not inhibit snail beta-mannosidase at 10 mM, but the alpha-mannoside mimic 18 inhibits Jack bean alpha-mannosidase (IC50 = 80 muM). These results are in keeping with the postulate that glycoside cleavage of beta-D-glycopyranosides requires a conformational change in agreement with the principle of stereoelectronic control.