(1S,4R,4aR,5S,8R,8aS)-8-(tert-Butyl-dimethyl-silanyloxy)-1,2,3,4-tetrachloro-9,9-dimethoxy-1,4,4a,5,8,8a-hexahydro-1,4-methano-naphthalen-5-ol | 188557-63-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1S,4R,4aR,5S,8R,8aS)-8-(tert-Butyl-dimethyl-silanyloxy)-1,2,3,4-tetrachloro-9,9-dimethoxy-1,4,4a,5,8,8a-hexahydro-1,4-methano-naphthalen-5-ol
• 英文别名: (1R,2R,3S,6R,7S,8S)-6-[tert-butyl(dimethyl)silyl]oxy-1,8,9,10-tetrachloro-11,11-dimethoxytricyclo[6.2.1.02,7]undeca-4,9-dien-3-ol
• CAS: 188557-63-3
• 化学式: C₁₉H₂₈Cl₄O₄Si
• 分子量: 490.326
• InChiKey: GSHDUDKSSIMLFH-XHSIOWMNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  28
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  47.9
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (1S,4R,4aR,5S,8R,8aS)-8-(tert-Butyl-dimethyl-silanyloxy)-1,2,3,4-tetrachloro-9,9-dimethoxy-1,4,4a,5,8,8a-hexahydro-1,4-methano-naphthalen-5-ol 在 chromium(VI) oxide 、 盐酸 、 甲醇 、 sodium tetrahydroborate 、 四氧化锇 、 N-甲基吲哚酮 、 cerium(III) chloride 、 camphor-10-sulfonic acid 、 potassium tert-butylate 、 lithium perchlorate 、 4-甲基苯磺酸吡啶 、 氢气 、 三氯化铁 、 四丁基碘化铵 、 potassium hydride 、 sodium hydride 、 三乙胺 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 甲醇 、 乙醚 、 水 、 丙酮 、 甲苯 为溶剂， 反应 72.5h， 生成 (1R,2R,3R,4S,4aR,7S,8aR)-2,4-Bis-benzyloxy-5-((S)-1-hydroxy-ethyl)-3-methyl-1,2,3,4,4a,7,8,8a-octahydro-naphthalene-1,7-diol
  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：

  (1S,2S,3R,6S,7R,8R)-1,8,9,10-tetrachloro-11,11-dimethoxy-3-pivaloyloxytricyclo[6.2.1.0^2,7]undeca-4,9-dien-6-ol 在 2,6-二甲基吡啶 、 sodium hydroxide 、 4-甲基苯磺酸吡啶 作用下， 以 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 生成 (1S,4R,4aR,5S,8R,8aS)-8-(tert-Butyl-dimethyl-silanyloxy)-1,2,3,4-tetrachloro-9,9-dimethoxy-1,4,4a,5,8,8a-hexahydro-1,4-methano-naphthalen-5-ol
  参考文献：
  名称：

  Desymmetrization of meso-Diols by Acylation with Axially Chiral Twisted Amides and Its Mechanistic Studies

  摘要：

  通过手性扭曲酰胺的酰化作用，实现了中-1,2-、-1,3-和-1,4-二醇的不对称化。1 为了阐明反应机理，通过优化PM3方法研究了扭曲酰胺的构象。酰胺键旋转的方向性被认为是立体选择性的重要原因。

  DOI：

  10.1246/cl.1998.995

文献信息

• Asymmetric Acylation of <i>s</i><i>ec</i>-Alcohols with Twisted Amides Possessing Axial Chirality Induced by the Adjacent Asymmetric Center
  作者：Shinji Yamada、Hiroko Katsumata

  DOI：10.1021/jo990892p

  日期：1999.12.1

  This paper reports that axially chiral twisted amides serve as asymmetric acylating agents for sec-alcohols under neutral conditions. Kinetic resolution of various racemic sec-alcohols and desymmetrization of 1,2-, 1,3-, and 1,4-meso-diols were performed by using the twisted amides. The utility of this desymmetrization method was shown by the preparation of the synthetic intermediate 28 for macrolide antibiotic nodusmicin and 18-deoxynargenicin. The stereoselectivity of the acylation reactions is significantly dependent on the bulkiness of both the acyl group and the C-4 substituent of the chiral auxiliary. When an amide possessing an imidazolyl group at C-4 was employed, the stereoselectivity was reversed to give R esters. A possible working model of the acylation reaction is also described on the basis of the structural studies of the twisted amides by IR and H-1 and C-13 NMR spectroscopies and AM1 calculations. These studies suggested that rotamer II is thermodynamically more stable than the others. The rotamer II has an axial chirality about its C(O)-N linkage that is induced by the adjacent chiral center. This would enable discrimination of the two enantiomeric hydroxy groups of the racemic alcohols or meso-diols.
• Untersuchungen zur Synthese des Nodusmicin, II: Synthese und Konformationsuntersuchung von 3,6-disubstituierten Tricyclo[6.2.1.02,7]undeca-4,9-dienen
  作者：Kurt Zimmermann

  DOI：10.1007/bf00810024

  日期：1993.11

  Ten 3,6-disubstituted tricyclo[6.2.1.0(2.7]undeca-4,9-dienes were prepared and their lowest energy conformations were found by molecular modelling and NMR-data. In 4 cases an X-ray crystal analysis confirmed the structure.
• 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.