(1R,2S,6S,7R,8R)-2-formyl-8-methyl-7-(triethylsiloxy)bicyclo[4.3.0]non-3-ene | 949585-51-7

• 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: (1R,2S,6S,7R,8R)-2-formyl-8-methyl-7-(triethylsiloxy)bicyclo[4.3.0]non-3-ene
• 英文别名: (1R,2R,3aS,4S,7aS)-2-methyl-1-triethylsilyloxy-2,3,3a,4,7,7a-hexahydro-1H-indene-4-carbaldehyde
• CAS: 949585-51-7
• 化学式: C₁₇H₃₀O₂Si
• 分子量: 294.51
• InChiKey: FVJQXWUQXBHXDQ-NQNKBUKLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.42
• 重原子数：
  20
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (R)-6-allyl-5,6-dihydro-3H-pyran-2,4-dione 、 (1R,2S,6S,7R,8R)-2-formyl-8-methyl-7-(triethylsiloxy)bicyclo[4.3.0]non-3-ene 、 2-甲氧基丙烯 在 ethylenediamine Tetraacetic Acid 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 3.0h， 生成 (4R,7R,1'R,2'R,4'S)-7-allyl-2-methoxy-2-methyl-4-[1'-(triethylsiloxy)-2'-methyl-2',3',3a',4',7',7a'-hexahydro-1H-inden-4'-yl]-3,4,7,8-tetrahydro-2H,5H-pyrano[4,3-b]pyran-5-one 、 (4S,7R,1'R,2'R,4'S)-7-allyl-2-methoxy-2-methyl-4-[1'-(triethylsiloxy)-2'-methyl-2',3',3a',4',7',7a'-hexahydro-1H-inden-4'-yl]-3,4,7,8-tetrahydro-2H,5H-pyrano[4,3-b]pyran-5-one
  参考文献：
  名称：

  走向耳蜗霉素和麦格霉素的结构分类的EPC合成。第3部分：EPC合成β-酮内酯亚基，并且首次尝试合成该组的五环抗生素

  摘要：

  提出了实用的EPC合成的δ-取代的-β-酮δ-内酯，耳蜗霉素和麦格霉素的亚基。结果，Tietze的串联反应被用于将δ-烯丙基-β-酮δ-内酯与氢化衍生物（这些产乙酸抗生素的第二个亚基）结合。最终氧化自由基串联环化反应的模型反应表明，亲电自由基仅以exo - trig方式环化。然而，用麦格霉素的预期前体，烯丙基氢的提取阻止了氧化自由基的串联环化。

  DOI：

  10.1016/j.tet.2007.05.093
• 作为产物：
  描述：

  (1R,3S,4R,6R,7R,8S)-3-(hydroxymethyl)-6-methyl-1-(tert-butyldimethylsiloxy)-10-oxatricyclo[5.2.1.0^4,8]decane 在 咪唑 、 丁硫醇 、 四丁基氟化铵 、 仲丁基锂 、 4-甲基苯磺酸吡啶 、 戴斯-马丁氧化剂 、 N,N-二异丙基乙胺 、 magnesium bromide 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 环己烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 12.5h， 生成 (1R,2S,6S,7R,8R)-2-formyl-8-methyl-7-(triethylsiloxy)bicyclo[4.3.0]non-3-ene
  参考文献：
  名称：

  Towards EPC-syntheses of the structural class of cochleamycins and macquarimicins. Part 2: EPC-synthesis of the hydrindene subunit of the macquarimicins

  摘要：

  The EPC-synthesis of the cis- hydrindene subunit of the macquarimicins, antibiotics with antitumour and anti-inflammatory activity, has been achieved. Desymmetrization of cis-1,4-cyclopent-2-enediol was succeeded by Diels-Alder reaction and functional group transformations to a tricyclic ketone. Regio- and stereoselective methylation via Claisen condensation and hydrogenation was followed by nucleophilic, intramolecular addition, reduction and acidic fragmentation. Further functional group transformations led to the target molecule. (c) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2007.05.094

文献信息

• Towards EPC-syntheses of the structural class of cochleamycins and macquarimicins. Part 2: EPC-synthesis of the hydrindene subunit of the macquarimicins
  作者：A. Chrobok、E. Gössinger、R. Kalb、E. Orglmeister、J. Schwaiger

  DOI：10.1016/j.tet.2007.05.094

  日期：2007.8

  The EPC-synthesis of the cis- hydrindene subunit of the macquarimicins, antibiotics with antitumour and anti-inflammatory activity, has been achieved. Desymmetrization of cis-1,4-cyclopent-2-enediol was succeeded by Diels-Alder reaction and functional group transformations to a tricyclic ketone. Regio- and stereoselective methylation via Claisen condensation and hydrogenation was followed by nucleophilic, intramolecular addition, reduction and acidic fragmentation. Further functional group transformations led to the target molecule. (c) 2007 Elsevier Ltd. All rights reserved.
• Towards EPC-syntheses of the structural class of cochleamycins and macquarimicins. Part 3: EPC-syntheses of the β-keto lactone subunits and first attempts towards the syntheses of the pentacyclic antibiotics of this group
  作者：A. Chrobok、E. Gössinger、K. Grünberger、H. Kählig、M.J. White、F. Wuggenig

  DOI：10.1016/j.tet.2007.05.093

  日期：2007.8

  Practical EPC-syntheses of δ-substituted-β-keto δ-lactones, subunits of the cochleamycins and macquarimicins, are presented. In consequence Tietze's tandem reaction is employed to combine δ-allyl-β-keto δ-lactone with a hydrindene derivative, the second subunit of these acetogenic antibiotics. Model reactions for the final oxidative radical tandem cyclization reveal that the electrophilic radical cyclizes

  提出了实用的EPC合成的δ-取代的-β-酮δ-内酯，耳蜗霉素和麦格霉素的亚基。结果，Tietze的串联反应被用于将δ-烯丙基-β-酮δ-内酯与氢化衍生物（这些产乙酸抗生素的第二个亚基）结合。最终氧化自由基串联环化反应的模型反应表明，亲电自由基仅以exo - trig方式环化。然而，用麦格霉素的预期前体，烯丙基氢的提取阻止了氧化自由基的串联环化。