7-Iodo-6,6,8-trimethyl-1,4-dithiaspiro[4.5]dec-7-ene | 173073-81-9

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫代缩醛
• 英文名称: 7-Iodo-6,6,8-trimethyl-1,4-dithiaspiro[4.5]dec-7-ene
• CAS: 173073-81-9
• 化学式: C₁₁H₁₇IS₂
• 分子量: 340.292
• InChiKey: WMTRFRNMJCQEAP-UHFFFAOYSA-N

物化性质

• 沸点：
  371.4±42.0 °C(Predicted)
• 密度：
  1.58±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  50.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  7-Iodo-6,6,8-trimethyl-1,4-dithiaspiro[4.5]dec-7-ene 在 manganese(IV) oxide 、 2-甲氧基丙烯 、 四丁基氟化铵 、 叔丁基锂 、 4-甲基苯磺酸吡啶 、 四氯化钛 、 calcium carbonate 、 mercury dichloride 、 锌 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 乙腈 、 苯 为溶剂， 反应 39.5h， 生成 (3aS,8S,9S,13bR)-2,2,5,14,14-pentamethyl-6,7,9,13b-tetrahydro-4,8-methanobenzo[3,4]cyclodeca[1,2-d][1,3]dioxole-8,9(3aH)-diol
  参考文献：
  名称：

  Taxane Synthesis through Intramolecular Pinacol Coupling at C-1−C-2. Highly Oxygenated C-Aromatic Taxanes

  摘要：

  Chiral, nonracemic intramolecular pinacol coupling substrates 3/20 and 30 have been prepared from ethyl isopropyl ketone and acryloyl chloride, which provide the A-ring and either o-iodobenzyl alcohol or 2,4-dimethoxybenzyl alcohol, which provide the respective aromatic C-rings, in 14-16 linear steps in overall yields of approximately 20%. Potential pinacol coupling substrate 23 could not be made available for investigation due to intervening pinacol rearrangement in the acetonide formation step. 3/20 undergo stereoselective cyclizations mediated by TiCl4-Zn in which the C-9 oxygen substituent plays the dominant role in determining the stereochemical outcome at C-l and C-2 in the respective tricyclic products 4 and 21. The formation of 21 is the more stereoselective process. The reagent of choice for the transformation of 30 into 31 is SmI2, which, although less stereoselective than TiCl4-Zn, leads to higher yielding carbon-carbon bond formation relative to carbonyl reduction. These pinacol cyclizations are interpreted to occur through endo boat-chair transition structures that prefer to orient the developing C-2 substituent and the preexisting C-9 substituent equatorially. Pinacol product 31 was converted through three additional steps into 40 having a B-ring closely related to that of taxol. We believe that these studies indicate pinacol cyclizations at C-1-C-2 to have considerable potential for producing advanced intermediates for syntheses of taxol and related complex taxanes.

  DOI：

  10.1021/jo9519367
• 作为产物：
  描述：

  1,2-乙二硫醇 、 5,5-(ethylenedioxy)-2,,6,6-trimethyl-1-iodocyclohexene 在 三氟化硼乙醚 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 生成 7-Iodo-6,6,8-trimethyl-1,4-dithiaspiro[4.5]dec-7-ene
  参考文献：
  名称：

  Taxane Synthesis through Intramolecular Pinacol Coupling at C-1−C-2. Highly Oxygenated C-Aromatic Taxanes

  摘要：

  Chiral, nonracemic intramolecular pinacol coupling substrates 3/20 and 30 have been prepared from ethyl isopropyl ketone and acryloyl chloride, which provide the A-ring and either o-iodobenzyl alcohol or 2,4-dimethoxybenzyl alcohol, which provide the respective aromatic C-rings, in 14-16 linear steps in overall yields of approximately 20%. Potential pinacol coupling substrate 23 could not be made available for investigation due to intervening pinacol rearrangement in the acetonide formation step. 3/20 undergo stereoselective cyclizations mediated by TiCl4-Zn in which the C-9 oxygen substituent plays the dominant role in determining the stereochemical outcome at C-l and C-2 in the respective tricyclic products 4 and 21. The formation of 21 is the more stereoselective process. The reagent of choice for the transformation of 30 into 31 is SmI2, which, although less stereoselective than TiCl4-Zn, leads to higher yielding carbon-carbon bond formation relative to carbonyl reduction. These pinacol cyclizations are interpreted to occur through endo boat-chair transition structures that prefer to orient the developing C-2 substituent and the preexisting C-9 substituent equatorially. Pinacol product 31 was converted through three additional steps into 40 having a B-ring closely related to that of taxol. We believe that these studies indicate pinacol cyclizations at C-1-C-2 to have considerable potential for producing advanced intermediates for syntheses of taxol and related complex taxanes.

  DOI：

  10.1021/jo9519367

文献信息

• Asymmetric Total Synthesis of Taxol
  作者：Ya-Jian Hu、Chen-Chen Gu、Xin-Feng Wang、Long Min、Chuang-Chuang Li

  DOI：10.1021/jacs.1c09637

  日期：2021.10.27

  bond formation. Furthermore, the existence of Taxol-resistant tumors and side effects of Taxol make the development of new approaches to synthesize Taxol and its derivatives highly desirable. Here, we report the asymmetric total synthesis of Taxol using a concise approach through 19 isolated intermediates. The synthetically challenging eight-membered ring was constructed efficiently by a diastereoselective

  紫杉醇是最著名的天然二萜类化合物之一，也是重要的抗癌药物。紫杉醇代表了一项艰巨的合成挑战，并引起了合成界的极大兴趣。然而，在以前的所有紫杉醇合成中，都没有关于通过 C1-C2 键形成闭合所需八元环的报道。此外，紫杉醇抗性肿瘤的存在和紫杉醇的副作用使得开发合成紫杉醇及其衍生物的新方法非常可取。在这里，我们使用简洁的方法通过 19 个分离的中间体报告了紫杉醇的不对称全合成。通过非对映选择性分子内 SmI 2有效构建了具有综合挑战性的八元环介导频哪醇偶联反应形成 C1-C2 键。独特的仿生氧烯反应和新开发的简便串联C2-苯甲酸酯形成和C13侧链安装提高了合成效率。光照条件下的温和氧烯反应将是涉及紫杉醇生物合成的替代反应。这种新的融合方法将允许紫杉醇衍生物的多样化创造，以实现进一步的生物学研究。
• 用于制备紫杉醇的中间体化合物及其合成方法以及紫杉醇的合成方法
  申请人：南方科技大学

  公开号：CN113880799B

  公开（公告）日：2022-10-11

  本发明涉及用于制备紫杉醇的中间体化合物及其合成方法以及紫杉醇的合成方法。所述用于制备紫杉醇的中间体化合物选自以下化合物中的至少一种：其中，Ts表示对甲苯磺酰基，TES表示三乙基硅基，TMS表示三甲基硅基，Ms表示甲磺酰基。以这些中间体化合物为原料可以高收率的制备得到紫杉醇，并容易对其结构进行修饰，可从中筛选出一系列先导化合物来研究其生物活性，相信会在肿瘤药物研发领域上有所突破。本发明的紫杉醇及其中间体的合成方法具有手性可控、收率高、产品纯度高、简洁高效的优点，并且原料来源广泛、试剂廉价易得、反应简单、操作简便、绿色环保、适合工业化放大生产。
• Pinacol closure of oxygenated taxane skeleta at C-1-C-2 with stereoinduction by oxygen substituents at C-9 and C-10
  作者：Charles S. Swindell、Weiming Fan、Peter G. Klimko

  DOI：10.1016/s0040-4039(00)73292-8

  日期：1994.7

  The treatment of keto aldehydes 4 and 5 with low-valent Ti results in stereoselective intramolecular pinacol couplings that lead to optically active oxygenated taxane skeleta 2 and 3.