3-C-acetylmethyl-3-deoxy-1,2:5,6-di-O-isopropylidene-α-D-allofuranose | 102561-96-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-C-acetylmethyl-3-deoxy-1,2:5,6-di-O-isopropylidene-α-D-allofuranose
• 英文别名: 1-[(3aR,5S,6R,6aR)-5-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyl-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxol-6-yl]propan-2-one
• CAS: 102561-96-6
• 化学式: C₁₅H₂₄O₆
• 分子量: 300.352
• InChiKey: FAILMCFSNKGHFU-UJPOAAIJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  21
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  63.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  3-C-acetylmethyl-3-deoxy-1,2:5,6-di-O-isopropylidene-α-D-allofuranose 在 镍 吡啶 、 sodium periodate 、 氢气 、 乙酸酐 、 溶剂黄146 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 pyridinium chlorochromate 作用下， 以 甲醇 、 乙醇 、 二氯甲烷 、 水 为溶剂， 反应 88.5h， 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 Optically Active 7-Oxabicyclo[4.3.0]non-4-en-3-one Skeleton from D-Glucose, and Its Transformation to Some Pseudo-Hexopyranoses

  摘要：

  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。

  DOI：

  10.1246/bcsj.60.1727
• 作为产物：
  描述：

  3-deoxy-3-C-(2-hydroxypropyl)-1,2:5,6-di-O-isopropylidene-α-D-allofuranose 在 molecular sieve 、 pyridinium chlorochromate 作用下， 以 二氯甲烷 为溶剂， 反应 18.0h， 生成 3-C-acetylmethyl-3-deoxy-1,2:5,6-di-O-isopropylidene-α-D-allofuranose
  参考文献：
  名称：

  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

  摘要：

  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。

  DOI：

  10.1246/bcsj.60.1727

文献信息

• Tandem intramolecular Michael addition/aldol condensation or acylation applied to D-glucose-derived substrates: preparation of enantiomeric octahydronaphthalenone derivatives equipped with C- and O-functionalities
  作者：Kinichi Tadano、Kensuke Nagashima、Yoshihide Ueno、Seiichiro Ogawa

  DOI：10.1021/jo00042a034

  日期：1992.7

  An enantiomerically pure (1,2-isopropylidenedioxy)tetrahydrofuran derivative, 9, bearing acetonyl and propionaldehyde side chains smoothly underwent aldol cyclization under basic conditions. The major product was the cis-aldol 21S, accompanied by the trans-diastereomer 21R in a ratio of 4 to 1. Further functionalized substrates 10 and 11, with either a (4-acetyl)- or a (4-ethoxycarbonyl)-3(E)-butenyl group, smoothly underwent a tandem Michael addition/aldol condensation or acylation by treatment with sodium hydride (NaH). In the case of 10, two cis-fused octahydronaphthalenones, 23 and 25, and a trans-fused diasteromer, 24, were isolated in 20%, 33%, and 11% yields, respectively. The substrate 11 provided a cis-substituted perhydrobenzofuran derivative, 26, and cis- and trans-fused octahydronaphthalenediones, 27 and 28, in 52%, 17%, and 9% yields, respectively. An intramolecular S(N)2' type cyclization of the corresponding 5-chloro-3(E)-pentenyl derivative, 14, provided exclusively (96%) the perhydrobenzofuran derivative, 29, in which the two newly introduced substituents are disposed in a cis relationship. The stereochemical assignments for each cyclization product were achieved by H-1 NMR analysis of the cyclization products or their chemically modified compounds. Preferential formation of the cis-fused carbocycles in the present studies is rationalized from a stereoelectronic viewpoint. Furthermore, the effect of substituents on the cyclization was investigated using two tetrahydrofuran derivatives, 20S and 20R. Base treatment of 20S gave the cis-fused tandem cyclization product 30 and the trans diastereomer 31 in a ratio of 3.8 to 1. In contrast, 20R gave two cyclization products, 32 and 33, in a ratio of 5 to 1, as a result of a preferential trans cyclization mode.