(3aR,7aS)-2,2-dimethyl-3a,4,7,7a-tetrahydrobenzo-1,3-dioxole | 65173-65-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (3aR,7aS)-2,2-dimethyl-3a,4,7,7a-tetrahydrobenzo-1,3-dioxole
• 英文别名: (3aR,7aS)-2,2-dimethyl-3a,4,7,7a-tetrahydro-1,3-benzodioxole
• CAS: 65173-65-1
• 化学式: C₉H₁₄O₂
• 分子量: 154.209
• InChiKey: WPUZTIGQTTXDIG-OCAPTIKFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (3aR,7aS)-2,2-dimethyl-3a,4,7,7a-tetrahydrobenzo-1,3-dioxole 在 吡啶 、 potassium permanganate 、 氧气 、 tetraphenylporphyrin 、 magnesium sulfate 、 硫脲 作用下， 以 甲醇 、 乙醇 、 二氯甲烷 、 水 为溶剂， 反应 36.0h， 生成
  参考文献：
  名称：

  A Convenient Synthesis of (±)-talo-Quercitol (1-Deoxy-neo-Inositol) and (±)-vibo-Quercitol (1-Deoxy-myo-Inositol) via Ene Reaction of Singlet Oxygen

  摘要：

  DOI：

  10.1021/jo971978q
• 作为产物：
  描述：

  1,4-环己二烯 在 四氧化锇 、 硫酸 、 N-甲基吗啉氧化物 作用下， 生成 (3aR,7aS)-2,2-dimethyl-3a,4,7,7a-tetrahydrobenzo-1,3-dioxole
  参考文献：
  名称：

  A Convenient Synthesis of (±)-talo-Quercitol (1-Deoxy-neo-Inositol) and (±)-vibo-Quercitol (1-Deoxy-myo-Inositol) via Ene Reaction of Singlet Oxygen

  摘要：

  DOI：

  10.1021/jo971978q

文献信息

• Optimisation of enantioselectivity for the chiral base-mediated rearrangement of bis-protected meso-4,5-dihydroxycyclohexene oxides: asymmetric synthesis of 4-deoxyconduritols and conduritol F
  作者：Simon E de Sousa、Peter O'Brien、Christopher D Pilgram

  DOI：10.1016/s0040-4020(02)00370-8

  日期：2002.6

  based on diastereoselective epoxidation of a cyclohexene followed by chiral lithium amide-mediated epoxide rearrangement has been used to synthesise an allylic alcohol building block of >95% ee. The key step is the enantioselective rearrangement of a bis-protected meso-4,5-dihydroxycyclohexene oxide. A range of protecting groups and chiral base structures were surveyed in order to find the optimum protocol

  一种基于环己烯的非对映选择性环氧化然后手性锂酰胺介导的环氧化物重排的策略已用于合成> 95％ee的烯丙醇结构单元。关键步骤是双保护的内消旋-4,5-二羟基环己烯氧化物的对映选择性重排。调查了一系列保护基团和手性碱基结构，以发现高对映选择性的最佳方案。使用叔丁基二甲基甲硅烷氧基保护基团和降麻黄碱衍生的手性碱，获得了> 95％ee的93％的烯丙醇收率。为了证明其合成实用性，该烯丙醇随后被转化为4-脱氧康杜糖醇和（+）-康杜糖醇F。
• A direct intramolecular asymmetric catalytic aldol cyclodehydration of meso-3,4-disubstituted-1,6-dialdehydes
  作者：Vanya B. Kurteva、Carlos A.M. Afonso

  DOI：10.1016/j.tet.2004.10.034

  日期：2005.1

  The intramolecular asymmetric catalytic aldol cyclodehydration of 1,6-dialdehydes to the corresponding cyclopentene carbaldehydes was accomplished for the first time on the cases of meso-3,4-disubstituted hexanedials. It was found that the presence of a hydroxyl group in the catalyst's molecule seems to be crucial to reach stereocontrol. The chiral centre, bearing the carboxylate functionality, in hydroxy

  在内消旋-3,4-二取代的己二醛的情况下，首次完成了1,6-二醛分子内不对称催化醛醇缩合反应生成相应的环戊烯甲醛。发现在催化剂分子中羟基的存在似乎对于达到立体控制至关重要。羟基氨基酸中带有羧酸盐官能团的手性中心控制最终产物的立体化学。对于氨基醇，其中不存在羧酸酯官能团，与羟基连接的碳的构型似乎是关键。另外，已经观察到手性膦和亚磷酸酯是该环脱水的有效催化剂，但是没有诱导立体控制。
• Simple Designs for the Construction of Complex trans-Fused Polyether Toxin Frameworks. A Linear Strategy Based on Entropically Favored Oxirane Ring Enlargement in Epoxycycloalkenes Followed by Carbon-Carbon or Carbon-Oxygen Bond-Forming Cyclizations
  作者：Eleuterio Alvarez、Maria T. Diaz、Ricardo Perez、Jose L. Ravelo、Alicia Regueiro、Jose A. Vera、Dacil Zurita、Julio D. Martin

  DOI：10.1021/jo00089a034

  日期：1994.5

  A successful design for the construction of trans-fused medium-size cyclic ethers is described. The key features of the synthesis are as follows: (i) intramolecular oxirane ring expansion in cycloalkenes to give bridged oxabicyclic systems and (ii) linear, one- or two-directional synthetic operations which generate external oxocycles in single reaction steps. The general approach involves the intramolecular addition of a stable gamma-alkoxy-substituted allylstannane to an aldehyde carbonyl group, and the entire reaction is conducted in a one-pot process which includes the following: (i) vic-diol fragmentation from the bridged oxabicyclic precursor and (ii) Lewis acid-induced cyclization of the resulting aldehyde-allylic tin system. While the present strategy was mostly developed around racemic models, the potential for adoption of;enantioselective features is immediate. The versatility, scope, limitations, and potential applications of the present technology are discussed in detail.
• Unexpected effect of protecting group and solvent on the stereoselectivity of m-CPBA epoxidation of diprotected cis-4,5-dihydroxycyclohexenes
  作者：Simon E. de Sousa、Alex Kee、Peter O'Brien、Simon T. Watson

  DOI：10.1016/s0040-4039(98)02319-3

  日期：1999.1

  The stereoselectivity of m-CPBA epoxidation of diprotected cis-4,5-dihydroxycyclohexenes has been studied as a function of protecting group. solvent and in one example, epoxidising reagent. Three different ways of obtaining high levels of trans diastereoselectivity have been uncovered. In addition, the results suggest that bulky silyl protecting groups (eg triethylsilyl and tert-butyldimethylsilyl) can, in CH2Cl2, behave as moderate cis-directors via hydrogen bonding to m-CPBA. (C) 1998 Elsevier Science Ltd. All rights reserved.