(+/-)-(1R*,5R*,6R*,7S*,8R*,9R*,10R*)-5-Acetyl-7,9-dibenzyloxy-10-hydroxy-8-methylbicyclo<4.4.0>decan-3-on

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (+/-)-(1R*,5R*,6R*,7S*,8R*,9R*,10R*)-5-Acetyl-7,9-dibenzyloxy-10-hydroxy-8-methylbicyclo<4.4.0>decan-3-on
• 英文别名: (4R,4aR,5S,6R,7R,8R,8aR)-4-acetyl-8-hydroxy-6-methyl-5,7-bis(phenylmethoxy)-3,4,4a,5,6,7,8,8a-octahydro-1H-naphthalen-2-one
• 化学式: C₂₇H₃₂O₅
• 分子量: 436.548
• InChiKey: YECFYBNEWIWRMK-USUVCMHUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  32
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  72.8
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (+/-)-(1R*,5R*,6R*,7S*,8R*,9R*,10R*)-5-Acetyl-7,9-dibenzyloxy-10-hydroxy-8-methylbicyclo<4.4.0>decan-3-on 在 palladium on activated charcoal 氢气 、 三乙胺 、 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 、 异丙醚 为溶剂， 反应 16.33h， 生成 1-[(1S,3S,4S,5R,6S,7S,8S,9S)-1-(tert-Butyl-dimethyl-silanyloxy)-5,7-bis-methoxymethoxy-6-methyl-11-oxa-tricyclo[6.2.1.0^4,9]undec-3-yl]-ethanone
  参考文献：
  名称：

  EPC合成Nodusmicin的方法-III。球菌霉素氧桥联十氢萘部分的制备

  摘要：

  从不饱和的1，4-间-二醇开始，对映体纯的4-甲硅烷氧基烯酮通过非对映体的缩醛和平衡来高收率地制备。烯酮以片段化为关键步骤转化为顺式十氢化萘酮衍生物。因此，根据反应条件的不同，氧化成共轭二烯，还原成烯二醇和分子内的氧化汞反应会产生不饱和的三环醚（构成与已知的18-脱氧纳那菌素合成的链接）或饱和的三环醚（代表起始化合物）用于构建根瘤霉素十元环的材料。

  DOI：

  10.1016/s0040-4020(97)00065-3
• 作为产物：
  描述：

  溴甲苯 在 盐酸 、 camphor-10-sulfonic acid 、 lithium perchlorate 、 四丁基碘化铵 、 sodium hydride 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 乙醚 、 水 、 甲苯 为溶剂， 反应 10.0h， 生成 (+/-)-(1R*,5R*,6R*,7S*,8R*,9R*,10R*)-5-Acetyl-7,9-dibenzyloxy-10-hydroxy-8-methylbicyclo<4.4.0>decan-3-on
  参考文献：
  名称：

  Untersuchungen zur Synthese des Nodusmicin, I: Darstellung von (�)-(1R*,5R*,6R*,7S*8R*,9R*,10R*)-5-Acetyl-7,9-dibenzyloxy-10-hydroxy-8-methylbicyclo[4.4.0]decan-3-on

  摘要：

  Our first target on the way towards the synthesis of nodusmicin is the preparation of the title compound. Meso diol 1 is partially etherified, then oxidized to the enone. The sterically compressed structure of this compound is the rationale of the highly stereoselective introduction of the substituents. (CH3)2CuLi introduces the methyl group and the enolate is captured as silylenol ether, which in turn is transformed to the alpha-hydroxyketone by OsO4. Reduction leads to the vicinal trans diol. Protection of the exo-hydroxy group is followed by treatment with sodium in ethanol. Via intramolecular nucleophilic addition, substitution and dechlorination the tetracyclic diketal 8 is formed. After exchange of the protective groups and partial hydrolysis of the ketals the tertiary alkohol is obtained with methyl Grignard reagent. Acidic fragmentation yields the desired title compound.

  DOI：

  10.1007/bf00816420

文献信息

• Approach towards an EPC synthesis of nodusmicin. Part 5: 1 Stereoselective introduction of a side chain at the cis -decalin part of nodusmicin
  作者：Edda Gössinger、Alexander Schwartz、Natascha Sereinig

  DOI：10.1016/s0040-4020(01)00155-7

  日期：2001.4

  were developed. Formation of the β-iodoacetal of the cyclic allylic alcohol 21 permitted intramolecular radical addition generating the desired configuration at C-4 of the decalin. Likewise formation of the β bromoacetal with the exo-cyclic hydroxy group of tricycle 12 led via SN2-reaction to tetrahydropyrans with the desired configuration at C-4. The oxygen bridge was introduced by dehydration of the

  据报道，顺式十氢化萘2的C-4侧链的引入和氧桥的关闭。2的部分脱氢后，进行氧合汞和卤素-汞交换。从三环化合物7a和7b的凸面发生丙烯酸酯之间的分子间自由基加成。连续差向异构化失败。因此，开发了两种使用分子内附接侧链的方法。环状烯丙醇21的β-碘缩醛的形成允许分子内自由基加成在十氢化萘的C-4处产生期望的构型。与exo同样形成β溴乙缩醛三轮车12的-环羟基经由S N 2-反应引导至在C-4具有所需构型的四氢吡喃。通过环外醇的脱水和连续的氧化汞来引入氧桥。汞-氧交换完成了反应顺序。
• Approach towards an EPC synthesis of nodusmicin — III. Preparation of the oxygen bridged decalin part of nodusmicin
  作者：Edda Gössinger、Michael Graupe、Christoph Kratky、Kurt Zimmermann

  DOI：10.1016/s0040-4020(97)00065-3

  日期：1997.3

  ether , which constitutes a link to a known 18-deoxynargenicin synthesis, or the saturated tricyclic ether , which represents the starting material for the construction of the tenmembered ring of nodusmicin.

  从不饱和的1，4-间-二醇开始，对映体纯的4-甲硅烷氧基烯酮通过非对映体的缩醛和平衡来高收率地制备。烯酮以片段化为关键步骤转化为顺式十氢化萘酮衍生物。因此，根据反应条件的不同，氧化成共轭二烯，还原成烯二醇和分子内的氧化汞反应会产生不饱和的三环醚（构成与已知的18-脱氧纳那菌素合成的链接）或饱和的三环醚（代表起始化合物）用于构建根瘤霉素十元环的材料。
• Untersuchungen zur Synthese des Nodusmicin, I: Darstellung von (�)-(1R*,5R*,6R*,7S*8R*,9R*,10R*)-5-Acetyl-7,9-dibenzyloxy-10-hydroxy-8-methylbicyclo[4.4.0]decan-3-on
  作者：E. G�ssinger、M. Graupe、K. Zimmermann

  DOI：10.1007/bf00816420

  日期：——

  Our first target on the way towards the synthesis of nodusmicin is the preparation of the title compound. Meso diol 1 is partially etherified, then oxidized to the enone. The sterically compressed structure of this compound is the rationale of the highly stereoselective introduction of the substituents. (CH3)2CuLi introduces the methyl group and the enolate is captured as silylenol ether, which in turn is transformed to the alpha-hydroxyketone by OsO4. Reduction leads to the vicinal trans diol. Protection of the exo-hydroxy group is followed by treatment with sodium in ethanol. Via intramolecular nucleophilic addition, substitution and dechlorination the tetracyclic diketal 8 is formed. After exchange of the protective groups and partial hydrolysis of the ketals the tertiary alkohol is obtained with methyl Grignard reagent. Acidic fragmentation yields the desired title compound.