3β-(Triisopropylsiloxy)-11α-hydroxy-3,4,8-epi-17,18-dinoraphidicol-6-en-16-one | 171625-51-7

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: 3β-(Triisopropylsiloxy)-11α-hydroxy-3,4,8-epi-17,18-dinoraphidicol-6-en-16-one
• 英文别名: (3S,4S,11R)-17,19-dinor-8-epi-11-hydroxy-3-(triisopropylsilyloxy)aphidicol-6-en-16-one；(3S,11R)-17,19-dinor-8-epi-11-hydroxy-3-(triisopropylsilyloxy)aphidicol-6-en-16-one；(1S,2S,5S,6S,7S,10S,12R,16R)-16-hydroxy-2,6-dimethyl-5-tri(propan-2-yl)silyloxytetracyclo[10.3.1.01,10.02,7]hexadec-8-en-13-one
• CAS: 171625-51-7
• 化学式: C₂₇H₄₆O₃Si
• 分子量: 446.746
• InChiKey: GKXWJKSJLWSEHR-VNAATSLESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.52
• 重原子数：
  31
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3β-(Triisopropylsiloxy)-11α-hydroxy-3,4,8-epi-17,18-dinoraphidicol-6-en-16-one 在 lithium carbonate 、 双(三甲基硅烷基)氨基钾 、 间氯过氧苯甲酸 、 APTS 作用下， 以 四氢呋喃 、 二氯甲烷 、 甲苯 为溶剂， 反应 11.41h， 生成 (3S,4S,11R,16R)-8-epi-11,16-[(S)-ethylidene]dioxy-19-nor-3-(triisopropylsilyloxy)aphidicol-6-en-17-ol
  参考文献：
  名称：

  通过串联环过环Diels-Alder / aldol反应合成蚜虫和非天然（11R）-（-）-8-epi-11-羟基蚜虫的全部不对称合成的新方法。

  摘要：

  在一个关键的反应中，由反式-反式-三烯大环（4）的高度非对映选择性串联的环式Diels-Alder（TADA）-醛醇缩合反应形成了8-表二十二烷骨架（3）。因此，构建了非天然衍生物（11R）-（-）-8-epi-11-羟基aphidicolin（2），并提出了解决许多Aphidicolin（1）合成的C16功能化问题的原始方法。

  DOI：

  10.1021/jo0007635
• 作为产物：
  描述：

  (14SR)-(1E,7E,9E)-(5S,6S)-14-(Methoxycarbonyl)-5-(triisopropylsiloxy)-2,6-dimethyl-1-<<(p-methoxybenzyl)oxy>methyl>-1,7,9-cyclopentadecatrien-13-one 在 咪唑 、 氰化钠 、 戴斯-马丁氧化剂 、 二甲基亚砜 、 三乙胺 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 二氯甲烷 、 水 、 甲苯 为溶剂， 反应 29.75h， 生成 3β-(Triisopropylsiloxy)-11α-hydroxy-3,4,8-epi-17,18-dinoraphidicol-6-en-16-one
  参考文献：
  名称：

  Transannular Diels-Alder/Intramolecular Aldol Tandem Reaction as a Stereocontrolled Route to (+)-Aphidicolin and its Isosteric C8-Epimer1

  摘要：

  The trans,syn,cis A.B.C.[6.6.7] tricyclic subunit of aphidicolin could be derived from the transannular Diels-Alder (TADA) reaction of a trans,cis,cis (TCC) cyclopentadecatriene. On the other hand, a trans,trans,cis (TTC) isomeric cyclopentadecatriene could lead to the trans,syn,trans tricyclic skeleton of aphidicolin's C8-epimer. Interestingly, semiempirical calculations have shown the latter to be isosteric with aphidicolin in respect to the four hydroxyl groups. The required TCC and TTC 15-membered macrocyclic trienes 46 and 59 were synthesized using modern methods of acyclic stereoselection such as an organocopper-based difunctionalization reaction, Evans' asymmetric aldol methodology and Wittig-Horner-Wadsworth reactions. At the end, an efficient macrocyclization protocol served in achieving the synthesis of the desired optically active precursors 46 and 59. Whereas TCC substrate 46 failed to realize a TADA cycloaddition for steric and conformational reasons, TTC cyclopentadecatrienal 59 led to a stereospecific TADA/aldol tandem reaction. In the first reported example of such a transformation, macrocycle 59 was thermolyzed (toluene, sealed tube, 210 degrees C, 18 h) in a single operation into tetracyclic product 61 containing six new stereogenic centers. Mechanistic considerations of this impressive conversion along with transition-state modeling are also presented. Further transformations of compound 61 culminating in stereospecific functionalization at C16 were performed by making use of an hydroxyl-directed epoxidation reaction leading to the advanced intermediate 67. Thus, this exploratory work demonstrates the value of a TADA/aldol route for the synthesis of the titled compounds and analogs thereof.

  DOI：

  10.1021/jo00129a021

文献信息

• Total Asymmetric Synthesis of the Aphidicolin Derivative (11<i>R</i>)-(−)-8-Epi-11-hydroxyaphidicolin Using Tandem Transannular Diels−Alder/Aldol Reactions
  作者：Guillaume Bélanger、Pierre Deslongchamps

  DOI：10.1021/ol990341l

  日期：2000.2.1

  [reaction: see text] Aphidicolin unnatural derivative (2) was synthesized using a new tandem transannular Diels-Alder/aldol methodology. The 8-epi-aphidicolane skeleton is constructed in a highly diastereoselective manner and converted into (11R)-(-)-8-epi-11-hydroxyaphidicolin (2). An efficient method for the difficult C16 funtionalization is presented.

  [反应：见正文]使用新的串联跨环形Diels-Alder / aldol方法合成了Aphidicolin非天然衍生物（2）。以高度非对映选择性的方式构建8-表观双环烷骨架，并将其转化为（11R）-（-）-8-表-11-羟基两环素（2）。提出了一种用于困难的C16功能化的有效方法。