5,5-(ethylenedioxy)-2,,6,6-trimethyl-1-iodocyclohexene | 150966-58-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 5,5-(ethylenedioxy)-2,,6,6-trimethyl-1-iodocyclohexene
• 英文别名: 7-iodo-6,6,8-trimethyl-1,4-dioxaspiro[4.5]dec-7-ene
• CAS: 150966-58-8
• 化学式: C₁₁H₁₇IO₂
• 分子量: 308.159
• InChiKey: LORPAOZLAQIUFI-UHFFFAOYSA-N

物化性质

• 沸点：
  312.2±42.0 °C(Predicted)
• 密度：
  1.54±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 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：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  5,5-(ethylenedioxy)-2,,6,6-trimethyl-1-iodocyclohexene 在 盐酸 作用下， 以 四氢呋喃 为溶剂， 以96%的产率得到3-iodo-2,2,4-trimethylcyclohex-3-en-1-one
  参考文献：
  名称：

  A concise synthesis of a highly functionalized C-aryl taxol analog by an intramolecular Heck olefination reaction

  摘要：

  A palladium(0) catalyzed intramolecular Heck olefination used to establish the C-10-C-11 connection in a highly functionalized taxane analog is described.

  DOI：

  10.1016/s0040-4039(00)79301-4
• 作为产物：
  描述：

  2,2-二甲基-1,3-环己烷二酮 在 camphor-10-sulfonic acid 、 1,5-二氮杂双环[4.3.0]壬-5-烯 、 碘 、 一水合肼 、 三乙胺 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 乙醚 、 乙醇 、 甲苯 为溶剂， 反应 19.5h， 生成 5,5-(ethylenedioxy)-2,,6,6-trimethyl-1-iodocyclohexene
  参考文献：
  名称：

  通过分子间和分子内自由基偶联反应实现紫杉醇的全合成

  摘要：

  紫杉醇是一种抗癌药物，具有异常氧化和错综复杂融合的 6/8/6/4 元环（ABCD 环）结构。在这里，我们报告了 34 步的紫杉醇全合成。分子间和分子内自由基偶联反应分别允许连接 A 环和 C 环以及环化 B 环。然后通过新设计的功能和保护基团操作将 ABC 环转化为目标。

  DOI：

  10.1002/anie.202219114

文献信息

• A concise enantioselective synthesis of a fully oxygen substituted ring A taxol precursor
  作者：Olivier Roy、Gerald Pattenden、David C. Pryde、Claire Wilson

  DOI：10.1016/s0040-4020(03)00699-9

  日期：2003.6

  A concise synthesis of the oxygen substituted ring A compound 2 found in Taxol®1a and Taxotere®1b starting from 2,2-dimethylcyclohexane-1,3-dione and proceeding via the key intermediates 8 and 11, is described. The absolute configuration of 2 was established from an X-ray crystal structure determination of a 4-bromophenylbenzoate derivative, viz. 15.

  氧取代的环的化合物的合成简明2紫杉醇发现® 1A和泰索帝® 1B经由关键中间体由2,2-二甲基环己烷-1,3-二酮和程序开始8和11，进行说明。根据X-射线晶体结构测定4-溴苯基苯甲酸酯衍生物，即2，确定2的绝对构型。15。
• Lipase-mediated resolution of the hydroxy-cyclogeraniol isomers: application to the synthesis of the enantiomers of karahana lactone, karahana ether, crocusatin C and γ-cyclogeraniol
  作者：Stefano Serra、Francesco G. Gatti、Claudio Fuganti

  DOI：10.1016/j.tetasy.2009.05.013

  日期：2009.6

  study on the lipase PS-mediated resolution of different hydroxy-geraniol isomers is reported. A number of α-, β- and γ-isomers bearing a 2-, 3- or 4-hydroxy functional group were synthesised regioselectively and then submitted to the lipase-mediated kinetic acetylation. The latter experiments showed that the 2-hydroxy isomers 4, 5 and 14 (α, γ and β, respectively) as well as cis-3-hydroxy α-cyclogeraniol

  报道了对脂肪酶PS介导的不同羟基香叶醇异构体拆分的综合研究。选择性地合成许多带有2-，3-或4-羟基官能团的α-，β-和γ-异构体，然后进行脂肪酶介导的动力学乙酰化。后者实验表明，2-羟基异构体4，5和14（α，γ分别和β），以及顺式-3-羟基α-cyclogeraniol 7和顺式-4-羟基γ-cyclogeraniol 10可以很容易地通过此过程解决。这些化合物主要部分的对映体纯度通过重结晶而提高，所得对映体二醇被用作合成天然萜类化合物卡拉汉内酯，卡拉汉醚和番红花素C的组成部分，并用于制备合成中间体γ-环香叶醇。二醇的对映异构体的绝对构型7，10，14和19通过用已知化合物的化学相关性来确定40，41，39和41分别。
• Total Synthesis of (±)-Kellermanoldione: Stepwise Cycloaddition of a Functionalized Diene and Allenoate
  作者：Michael E. Jung、Jesus Cordova、Masayuki Murakami

  DOI：10.1021/ol901455q

  日期：2009.9.3

  The total synthesis of the diterpene kellermanoldione 1 is reported. Stepwise [4 + 2] cycloaddition of the ketal diene 8 and the allenoate 3 afforded the exo adduct 10x as the major product. It was converted into 1 via six steps, among them a key nonconjugative hydrolysis of a γ-methylene silyl enol ether.

  据报道，二萜kellermanoldione 1的全合成。缩酮二烯8和烯丙酸酯3的逐步[4 + 2]环加成提供了exo加合物10x作为主要产物。通过六个步骤将其转化为1，其中关键是γ-亚甲基甲硅烷基烯醇醚的非共轭水解。
• Total Synthesis of 1‐Hydroxytaxinine
  作者：Yusuke Imamura、Shun Yoshioka、Masanori Nagatomo、Masayuki Inoue

  DOI：10.1002/anie.201906872

  日期：2019.8.26

  Abstract1‐Hydroxytaxinine (1) is a cytotoxic taxane diterpenoid. Its central eight‐membered B‐ring possesses four oxygen‐functionalized centers (C1, C2, C9, and C10) and two quaternary carbon centers (C8 and C15), and is fused with six‐membered A‐ and C‐rings. The densely functionalized and intricately fused structure of 1 makes it a highly challenging synthetic target. Reported here is an efficient radical‐based strategy for assembling 1 from A‐ and C‐ring fragments. The A‐ring bearing an α‐alkoxyacyl telluride moiety underwent intermolecular coupling with the C‐ring fragment by a Et3B/O2‐promoted decarbonylative radical formation. After construction of the C8‐quaternary stereocenter, a pinacol coupling reaction using a low‐valent titanium reagent formed the B‐ring with stereoselective installation of the C1,C2‐diol. Subsequent manipulations at the A‐ and C‐rings furnished 1 in 26 total steps.
• Taxane Synthesis through Intramolecular Pinacol Coupling at C-1−C-2. Highly Oxygenated C-Aromatic Taxanes
  作者：Charles S. Swindell、Weiming Fan

  DOI：10.1021/jo9519367

  日期：1996.1.1

  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.