(1R,6R,8R,9R)-8,9-(isopropylidenedioxy)-7-oxabicyclo<4.3.0>nonan-3-one | 102562-00-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1R,6R,8R,9R)-8,9-(isopropylidenedioxy)-7-oxabicyclo<4.3.0>nonan-3-one
• 英文别名: (3aR,4aR,8aR,8bR)-2,2-dimethyl-4a,5,6,8,8a,8b-hexahydro-3aH-[1,3]dioxolo[4,5-b][1]benzofuran-7-one
• CAS: 102562-00-5
• 化学式: C₁₁H₁₆O₄
• 分子量: 212.246
• InChiKey: GDIXKODPQDQDHT-ZYUZMQFOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  15
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  (3R,6R,8R,9R)-8,9-(isopropylidenedioxy)-7-oxabicyclo<4.3.0>non-1-en-3-ol 在 Raney nickel T-4 molecular sieve 、 氢气 、 pyridinium chlorochromate 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 28.0h， 生成 (1R,6R,8R,9R)-8,9-(isopropylidenedioxy)-7-oxabicyclo<4.3.0>nonan-3-one
  参考文献：
  名称：

  Construction of an enantiomerically pure cis-fused 7-oxabicyclo[4.3.0]nonan-3-one skeleton. Synthesis of (1S,6R,8R,9R)-8,9-(isopropylidenedioxy)-7-oxabicyclo[4.3.0]nonan-3-one from D-allose

  摘要：

  DOI：

  10.1021/jo00242a049

文献信息

• Construction of an Optically Active 7-Oxabicyclo[4.3.0]non-4-en-3-one Skeleton from D-Glucose, and Its Transformation to Some Pseudo-Hexopyranoses
  作者：Kin-ichi Tadano、Yoshihide Ueno、Chiyoko Fukabori、Yukinori Hotta、Tetsuo Suami

  DOI：10.1246/bcsj.60.1727

  日期：1987.5

  A versatile chiral compound, (1R,6R,8R,9R)-8,9-isopropylidenedioxy-7-oxabicyclo[4.3.0]non-4-en-3-one (6), was efficiently synthesized from d-glucose. The synthesis featured an intramolecular aldol cyclization of 3-C-acetylmethyl-3-deoxy-1,2-O-isopropylidene-α-d-ribo-pentodialdo-1,4-furanose, which was readily derivatized from the known Wittig adducts of 1,2:5,6-di-O-isopropylidene-α-d-ribo-hexofuranos-3-ulose. The utility of this highly functionalized chiral synthon 6 was embodied by conversion to four optically active pseudosugars, these are pentaacetyl derivatives of pseudo-α-l-altropyranose, pseudo-β-d-glucopyranose, pseudo-2-amino-2-deoxy-β-l-altropyranose, and pseudo-2-amino-2-deoxy-α-d-glucopyranose (a derivative of pseudoglucosamine). The transformation of 6 to the pseudo sugars involved 1) a stereospecific epoxidation of the double bond in 6 providing (1R,4S,5S,6S,8R,9R)-4,5-epoxy-8,9-isopropylidenedioxy-7-oxabicyclo[4.3.0]nonan-3-one (8), and 2) an exclusive diaxial ring opening of the β-epoxy alcohols, which were derived from 8, providing (1R,3R,4S,5S,6S,8R,9R)-8,9-isopropylidenedioxy-7-oxabicyclo[4.3.0]nonane-3,4,5-triol (11) or (1R,3S,4S,5R,6S,8R,9R)-4-azido-8,9-isopropylidenedioxy-7-oxabicyclo[4.3.0]nonane-3,5-diol. Treatment of (1R,2S,3S,4S,5R)-3,4,5-tris(benzyloxy)-2-hydroxycyclohexanecarbaldehyde, which was derived from 11, with methanesulfonyl chloride, and successive sodium borohydride reduction provided (3S,4S,5R)-3,4,5-tris(benzyloxy)-1-cyclohexene-1-methanol (19). Hydroboration of 19 proceeded from the less hindered side stereoselectively.

  以 d-葡萄糖为原料，高效合成了一种多功能手性化合物 (1R,6R,8R,9R)-8,9-异丙叉二氧基-7-氧杂二环[4.3.0]non-4-en-3-one (6)。该合成以 3-C-乙酰甲基-3-脱氧-1,2-O-异丙叉-α-d-核糖-戊二醛-1,4-呋喃糖的分子内羟醛环化为特征，很容易从已知的 Wittig 加合物衍生而来1,2:5,6-二-O-异亚丙基-α-d-核糖-六呋喃-3-乌糖。这种高度功能化的手性合成子 6 的实用性通过转化为四种光学活性假糖来体现，它们是假-α-L-吡喃丙醇糖、假-β-d-吡喃葡萄糖、假-2-氨基-2-脱氧-的五乙酰衍生物。 β-l-吡喃丙糖和假-2-氨基-2-脱氧-α-d-吡喃葡萄糖（假葡萄糖胺的衍生物）。 6 向假糖的转化涉及 1) 6 中双键的立体特异性环氧化，提供 (1R,4S,5S,6S,8R,9R)-4,5-环氧-8,9-异丙叉二氧基-7-氧杂双环[4.3.0]壬南-3-酮 (8)，和 2) β-环氧醇的独特双轴开环，衍生自 8，提供 (1R,3R,4S,5S,6S,8R,9R )-8,9-异丙叉二氧基-7-氧杂二环[4.3.0]壬烷-3,4,5-三醇(11)或(1R,3S,4S,5R,6S,8R,9R)-4-叠氮基-8 ,9-异丙叉二氧基-7-氧杂双环[4.3.0]壬烷-3,5-二醇。用甲磺酰氯处理衍生自11的(1R,2S,3S,4S,5R)-3,4,5-三(苄氧基)-2-羟基环己烷甲醛，并连续进行硼氢化钠还原，得到(3S,4S, 5R)-3,4,5-三(苄氧基)-1-环己烯-1-甲醇(19)。 19的硼氢化反应从受阻较小的一侧立体选择性地进行。
• A NOVEL SYNTHESIS OF PSEUDO-α-L-ALTROPYRANOSE FROM D-GLUCOSE
  作者：Tetsuo Suami、Kin-ichi Tadano、Yoshihide Ueno、Chiyoko Fukabori

  DOI：10.1246/cl.1985.1557

  日期：1985.10.5

  (1R,6R,8R,9R)-8,9-Isopropylidenedioxy-3-oxo-7-oxabicyclo[4.3.0]non-4-ene, a highly functionalized bicyclic compound, has been synthesized from D-glucose employing an intramolecular aldol condensation as the key reaction, and a transformation of it into pseudo-α-L-altropyranose was achieved efficiently.

  (1R,6R,8R,9R)-8,9-Isopropylidenedioxy-3-oxo-7-oxabicyclo[4.3.0]non-4-ene 是一种高度官能化的双环化合物，由 D-葡萄糖合成以羟醛缩合为关键反应，并有效地实现了将其转化为假α-L-吡喃丙二糖。
• Synthesis of annulated furanoses by free-radical cyclization of haloalkenes derived from diacetone glucose
  作者：Jose Marco-Contelles、Angeles Martinez-Grau、M. Martinez-Ripoll、H. Cano、C. Foces-Foces

  DOI：10.1021/jo00027a076

  日期：1992.1