(3aR,5S,6R,6aR)-2,2-Dimethyl-6-(2-oxo-propyl)-tetrahydro-furo[2,3-d][1,3]dioxole-5-carbaldehyde | 102561-98-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (3aR,5S,6R,6aR)-2,2-Dimethyl-6-(2-oxo-propyl)-tetrahydro-furo[2,3-d][1,3]dioxole-5-carbaldehyde
• 英文别名: (3aR,5S,6R,6aR)-2,2-dimethyl-6-(2-oxopropyl)-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxole-5-carbaldehyde
• CAS: 102561-98-8
• 化学式: C₁₁H₁₆O₅
• 分子量: 228.245
• InChiKey: HPWXNPIQKAYCDA-ZYUZMQFOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.2
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (3aR,5S,6R,6aR)-2,2-Dimethyl-6-(2-oxo-propyl)-tetrahydro-furo[2,3-d][1,3]dioxole-5-carbaldehyde 在 Raney nickel T-4 lithium aluminium tetrahydride 、 4 A molecular sieve 、 氢气 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 、 苯 为溶剂， 25.0 ℃ 、101.33 kPa 条件下， 反应 25.0h， 生成 (1R,3R,4R,5R)-3-<(3E)-4-(ethoxycarbonyl)-3-butenyl>-4-(2-oxopropyl)-7,7-dimethyl-2,6,8-trioxabicyclo<3.3.0>octane
  参考文献：
  名称：

  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

  摘要：

  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.

  DOI：

  10.1021/jo00042a034
• 作为产物：
  描述：

  1,2:5,6-di-O-isopropylidene-α-D-ribo-3-hexulofuranose 在 镍 sodium periodate 、 氢气 、 溶剂黄146 、 pyridinium chlorochromate 作用下， 以 甲醇 、 水 为溶剂， 生成 (3aR,5S,6R,6aR)-2,2-Dimethyl-6-(2-oxo-propyl)-tetrahydro-furo[2,3-d][1,3]dioxole-5-carbaldehyde
  参考文献：
  名称：

  由 D-葡萄糖合成假-α-L-吡喃丙酮糖的新方法

  摘要：

  (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。

  DOI：

  10.1246/cl.1985.1557

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。
• TADANO, KIN-ICHI;UENO, YOSHIHIDE;FUKABORI, CHIYOKO;HOTTA, YUKINORI;SUAMI,+, BULL. CHEM. SOC. JAP., 60,(1987) N 5, 1727-1739
  作者：TADANO, KIN-ICHI、UENO, YOSHIHIDE、FUKABORI, CHIYOKO、HOTTA, YUKINORI、SUAMI,+

  DOI：——

  日期：——