(1S,5R,6R)-6-[tert-butyl(dimethyl)silyl]oxy-1-ethenyl-2-methyl-5-prop-1-en-2-ylcyclohex-2-en-1-ol | 423764-39-0

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (1S,5R,6R)-6-[tert-butyl(dimethyl)silyl]oxy-1-ethenyl-2-methyl-5-prop-1-en-2-ylcyclohex-2-en-1-ol
• CAS: 423764-39-0
• 化学式: C₁₈H₃₂O₂Si
• 分子量: 308.536
• InChiKey: XPRHQIHHCUVUEW-NUJGCVRESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.84
• 重原子数：
  21
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1S,5R,6R)-6-[tert-butyl(dimethyl)silyl]oxy-1-ethenyl-2-methyl-5-prop-1-en-2-ylcyclohex-2-en-1-ol 在 乙烯基溴化镁 、 四丁基氟化铵 、 三异丙基硅基三氟甲磺酸酯 、 双(三甲基硅烷基)氨基钾 、 N,N-二异丙基乙胺 、 二苯二硫醚 作用下， 以 四氢呋喃 、 乙醚 、 氘代氯仿 、 二氯甲烷 、 甲苯 为溶剂， 反应 31.08h， 生成 4-[(5R,6R)-5-Isopropenyl-6-(2-methoxy-ethoxymethoxy)-2-methyl-cyclohex-2-en-(Z)-ylidene]-2,2-dimethyl-butyric acid methyl ester
  参考文献：
  名称：

  Intramolecularly Competitive Ireland-Claisen Rearrangements:  Scope and Potential Applications to Natural Product Synthesis

  摘要：

  A variety of bis-allylic esters were prepared by vinylmetal addition to cycloalkenones followed by esterification either in situ or in a separate operation. For chiral cyclohexenones, the vinyl additions generally occurred with > 10:1 diastereoselectivity. Although in some cases the bis-allylic esters proved to be sensitive to silica gel or other adsorbents, all of the esters examined could be isolated in acceptable purity. The Ireland-Claisen rearrangement of the bis-allylic esters occurred with complete regioselectivity via the exocyclic alkene. The alkene stereochemistry and the stereochemistry at C-2 and C-3 of the pentenoic acid products were consistent with a chairlike transition state in the rearrangement. Substituents at the carbons adjacent to the allylic carbinol carbon (i.e., C-2 or C-6 in cyclohexenone-derived substrates) directed the stereochemical course of the rearrangement. The rearrangements generally proceeded so as to place the larger of the C-2 or C-6 substituents in the pseudoequatorial position with respect to the chairlike transition state. For a bis-allylic ester bearing both a C-2-CH3 and a C-6-OMEM substituent, the rearrangement product resulted from the nominally smaller OMEM substituent occupying a pseudoequatorial position with respect to the chairlike transition state.

  DOI：

  10.1021/jo010752r
• 作为产物：
  描述：

  四乙烯基锡 、 (5R,6R)-6-[tert-butyl(dimethyl)silyl]oxy-2-methyl-5-prop-1-en-2-ylcyclohex-2-en-1-one 在 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 反应 7.0h， 以70%的产率得到(1S,5R,6R)-6-[tert-butyl(dimethyl)silyl]oxy-1-ethenyl-2-methyl-5-prop-1-en-2-ylcyclohex-2-en-1-ol
  参考文献：
  名称：

  Intramolecularly Competitive Ireland-Claisen Rearrangements:  Scope and Potential Applications to Natural Product Synthesis

  摘要：

  A variety of bis-allylic esters were prepared by vinylmetal addition to cycloalkenones followed by esterification either in situ or in a separate operation. For chiral cyclohexenones, the vinyl additions generally occurred with > 10:1 diastereoselectivity. Although in some cases the bis-allylic esters proved to be sensitive to silica gel or other adsorbents, all of the esters examined could be isolated in acceptable purity. The Ireland-Claisen rearrangement of the bis-allylic esters occurred with complete regioselectivity via the exocyclic alkene. The alkene stereochemistry and the stereochemistry at C-2 and C-3 of the pentenoic acid products were consistent with a chairlike transition state in the rearrangement. Substituents at the carbons adjacent to the allylic carbinol carbon (i.e., C-2 or C-6 in cyclohexenone-derived substrates) directed the stereochemical course of the rearrangement. The rearrangements generally proceeded so as to place the larger of the C-2 or C-6 substituents in the pseudoequatorial position with respect to the chairlike transition state. For a bis-allylic ester bearing both a C-2-CH3 and a C-6-OMEM substituent, the rearrangement product resulted from the nominally smaller OMEM substituent occupying a pseudoequatorial position with respect to the chairlike transition state.

  DOI：

  10.1021/jo010752r