2,3,4,7-tetra-O-benzyl-2-epi-5-epi-<6-2H2>valiolone | 244195-56-0

• 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: 2,3,4,7-tetra-O-benzyl-2-epi-5-epi-<6-2H2>valiolone
• 英文别名: 2,3,4,7-tetra-O-benzyl-2-epi-5-epi-(6-(2)H2)valiolone；(3R,4S,5S,6S)-2,2-dideuterio-3-hydroxy-4,5,6-tris(phenylmethoxy)-3-(phenylmethoxymethyl)cyclohexan-1-one
• CAS: 244195-56-0
• 化学式: C₃₅H₃₆O₆
• 分子量: 554.651
• InChiKey: JWXHKWBUBUUEFP-RQANGVAYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  41
• 可旋转键数：
  13
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  74.2
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2,3,4,7-tetra-O-benzyl-2-epi-5-epi-<6-2H2>valiolone 在 sodium tetrahydroborate 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 2.5h， 以86%的产率得到2,3,4,7-tetra-O-benzyl-1-epi-2-epi-5-epi-(6-(2)H2)valiolol
  参考文献：
  名称：

  Biosynthetic studies on the α-glucosidase inhibitor acarbose: the chemical synthesis of isotopically labeled 2-epi-5-epi-valiolone analogs

  摘要：

  2-epi-5-epi-Valiolone is a cyclization product of the C-7 sugar phosphate, sedoheptulose 7-phosphate, involved in the biosynthesis of the aminocyclitol moieties of acarbose, validamycin, and pyralomicin. As part of our investigation into the pathway from 2-epi-5-epi-valiolone to the valienamine moiety of acarbose, we prepared 1-epi-5-epi-(6-H-2(2))valiolol [(6-H-2(2))-6], 5-epi-(6-H-2(2))valiolol [(6-H-2(2))-17], 1-epi-2-epi-5-epi-(6-H-2(2))valiolol [(6-H-2(2))-12] and 2-epi-5-epi-(6-H-2(2))valiolamine [(6-H-2(2))-11]. Compounds (6-H-2(2))-6 and (6-H-2(2))-17 were synthesized from 2,3,4,6-tetra-O-benzyl-D-glucopyranose in 10 and seven steps, respectively, whereas (6-H-2(2))-12 and (6-H-2(2))-11 were synthesized from 2,3,4,6-tetra-O-benzyl-D-mannopyranose in eight and 10 steps, respectively. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/s0008-6215(03)00315-x
• 作为产物：
  描述：

  (2S,3S,4S,5RS)-2,3,4-tri-O-benzyl-5-C-<(benzyloxy)methyl>-6,6-dichloro-1-oxo-2,3,4,5-cyclohexanetetrol 在 偶氮二异丁腈 、 氘代三正丁基锡 作用下， 以 甲苯 为溶剂， 反应 2.0h， 生成 2,3,4,7-tetra-O-benzyl-2-epi-5-epi-<6-2H2>valiolone 、 2,3,4,7-tetra-O-benzyl-2-epi-<6-2H2>valiolone
  参考文献：
  名称：

  Biosynthetic Studies on the α-Glucosidase Inhibitor Acarbose in Actinoplanes sp.:  2-epi-5-epi-Valiolone Is the Direct Precursor of the Valienamine Moiety

  摘要：

  The biosynthetic pathway leading to the mC(7)N cyclitol (valienamine) moiety of acarbose (1) in Actinoplanes sp. strain SN 223/29 has been studied using H-3-, H-2-, and C-13-labeled cyclitols. These precursors were synthesized from D-glucose or D-mannose as starting materials. The feeding experiments demonstrated that cyclitols having the same stereochemistry at C-2 as the valienamine moiety of acarbose; i.e., valienone, valienamine, valiolone, valiolamine, and 1-epi-valienol, were not incorporated and thus are not plausible intermediates in 1 biosynthesis. 2-epi-Valiolone (10b), which has the same stereochemistry as the presumed open-chain precursor, sedoheptulose 7-phosphate, was also not incorporated. However, its C-5 epimer (10a) was incorporated efficiently and specifically into the valienamine moiety of 1. Surprisingly, the dehydrated form of 2-epi-5-epi-valiolone, 2-epi-valienone, was not incorporated. This suggests that 2-epi-5-epi-valiolone must be converted directly into the pseudodisaccharide moiety of acarbose without the intervention of other free cyclitol intermediates. This may occur by linkage to the amino group of TDP-4-amino-4,6-dideoxyglucose to form. the imine, epimerization at C-2 to the correct stereochemistry, dehydration between C-5 and C-6 aided by enamine formation, and finally reduction to the amine. It is proposed that these reaction steps all take place on a single enzyme without free intermediates. Alternative mechanistic possibilities are also discussed.

  DOI：

  10.1021/ja991102w