3,4-(isopropylidenedioxy)adipinaldehyde | 831228-25-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3,4-(isopropylidenedioxy)adipinaldehyde
• 英文别名: 2-[(4R,5S)-2,2-dimethyl-5-(2-oxoethyl)-1,3-dioxolan-4-yl]acetaldehyde
• CAS: 831228-25-2
• 化学式: C₉H₁₄O₄
• 分子量: 186.208
• InChiKey: DPOFKBYCHLPCDD-OCAPTIKFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.6
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3,4-(isopropylidenedioxy)adipinaldehyde 在 二异丁基氢化铝 作用下， 以 乙醚 为溶剂， 反应 1.0h， 以96%的产率得到2-[(4R,5S)-5-(2-Hydroxy-ethyl)-2,2-dimethyl-[1,3]dioxolan-4-yl]-ethanol
  参考文献：
  名称：

  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

  摘要：

  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.

  DOI：

  10.1021/jo00089a034
• 作为产物：
  描述：

  (3aR,7aS)-2,2-dimethyl-3a,4,7,7a-tetrahydrobenzo-1,3-dioxole 在 氧气 、 臭氧 、 二甲基硫 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 生成 3,4-(isopropylidenedioxy)adipinaldehyde
  参考文献：
  名称：

  内消旋-3,4-二取代-1,6-二醛的分子内不对称催化羟醛直接环脱水

  摘要：

  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。

  DOI：

  10.1016/j.tet.2004.10.034

文献信息

• Synthesis of cyclopentanthraquinones: analogs of mitomycin C
  作者：Bernd Kohler、Tsann Long Su、Ting Chao Chou、Xiang Jun Jiang、Kyoichi A. Watanabe

  DOI：10.1021/jo00059a014

  日期：1993.3

  2,3-Dihydro-1H-cyclopent[a]anthracene-6,11-dione (cyclopentanthraquinone) derivatives bearing a mustard side chain at C-4 and an aziridine ring at the cyclopentene moiety were synthesized. Such a compound may be viewed as an analogue of mitomycin C (MC) and may exhibit bifunctional DNA-alkylating and DNA-intercalating agent. The key intermediate, 4-hydroxy-2,3-di-O-substituted cyclopentanthraquinone, was synthesized by Deils-Alder reaction of naphthoquinone with various 4,5-dihydroxy-1-vinylcyclopent-1-ene derivatives. Introduction of a mustard side chain to the OH group at C-4 and subsequent construction of an aziridine-ring on C2-C3 of the cyclopentanthraquinone molecule furnished the target compound, 2,3-aziridino-4-[2-[NN-bis(2-chloroethyl)amino]ethoxy]-2,3-dihydro-1H-cyclopent [a] anthracene-6,11-dione (37). It was found that both the aziridine function and the mustard side chain play a significant role in their cytotoxicity against leukemic L1210 and HL-60 cell growth in culture and the inhibition of topoisomerase II kDNA decatenation.
• 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.
• 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。