rel-(4R,5S)-4-Hydroxy-4,7,9,9-tetramethylspiro<4.5>dec-7-en-1-one

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: rel-(4R,5S)-4-Hydroxy-4,7,9,9-tetramethylspiro<4.5>dec-7-en-1-one
• 英文别名: rel-(4R,5S)-4-Hydroxy-4,7,9,9-tetramethylspiro[4.5]dec-7-en-1-one
• 化学式: C₁₄H₂₂O₂
• 分子量: 222.327
• InChiKey: NJJAPHAJVKXCDU-ZIAGYGMSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.85
• 重原子数：
  16.0
• 可旋转键数：
  0.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  37.3
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为产物：
  描述：

  1,1-ethylenedioxy-3,5,5-trimethylcyclohex-3-ene 在 三氟化硼乙醚 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 2.0h， 生成 rel-(4R,5S)-4-Hydroxy-4,7,9,9-tetramethylspiro<4.5>dec-7-en-1-one
  参考文献：
  名称：

  Spiroannulation approach to pentalenene, an angular triquinane sesquiterpene

  摘要：

  The route to the angular triquinane (+/-)-pentalenene (la) followed from an efficient geminal acylation of the acetal of isophorone or its homolog 6b by 1,2-bis((trimethylsilyl) oxy) cyclobutene (3) in the presence of boron trifluoride etherate. Ring cleavage and reclosure (9 --> 11) secured the required spiro[4.4]nonane system with a pendant ketone function in place for the closure of the final, central : I ring. The relative stereochemistry at C-9 was established during hydrogenation over palladium of the C-3 double bond of 11, but the facial selectivity was determined by the mode of reduction of the conjugated, orthogonal double bond at C-6 of 11. After cyclization to the enone 17b, the synthesis was completed by reductions of both the double bond and the ketone and simple dehydration. The 9-epi isomer (26) of (+/-)-pentalenene was synthesized also.

  DOI：

  10.1021/jo00080a018

文献信息

• Facial selectivity in nucleophilic reactions of spirocyclic ketones can be controlled by a distant, orthogonal double bond
  作者：Pei-Ying Liu、D. Jean Burnell

  DOI：10.1039/c39940001183

  日期：——

  Spiro[4.5]dec-7-ene-1,4-dione and derivatives substituted at C-7, C-8, and/or C-9 gave products of reaction with methyllithium and with sodium borohydride that in every instance favoured nucleophilic carbonyl attack on the face syn to the double bond; the results are consistent with stereoelectronic control, and the selectivity correlates with a difference in the abilities of the orthogonal C–C bond to donate electron density.

  在C-7、C-8和/或C-9上被取代的螺[4.5]癸-7-烯-1,4-二酮及其衍生物与甲基锂和硼氢化钠反应，在每种情况下都倾向于对双键的同侧进行亲核羰基攻击；结果与立体电子控制一致，选择性与正交C-C键的供电子密度能力差异相关。
• Spiroannulation approach to pentalenene, an angular triquinane sesquiterpene
  作者：Y.-J. Wu、Y.-Y. Zhu、D. Jean Burnell

  DOI：10.1021/jo00080a018

  日期：1994.1

  The route to the angular triquinane (+/-)-pentalenene (la) followed from an efficient geminal acylation of the acetal of isophorone or its homolog 6b by 1,2-bis((trimethylsilyl) oxy) cyclobutene (3) in the presence of boron trifluoride etherate. Ring cleavage and reclosure (9 --> 11) secured the required spiro[4.4]nonane system with a pendant ketone function in place for the closure of the final, central : I ring. The relative stereochemistry at C-9 was established during hydrogenation over palladium of the C-3 double bond of 11, but the facial selectivity was determined by the mode of reduction of the conjugated, orthogonal double bond at C-6 of 11. After cyclization to the enone 17b, the synthesis was completed by reductions of both the double bond and the ketone and simple dehydration. The 9-epi isomer (26) of (+/-)-pentalenene was synthesized also.