6-acetoxi-7-(trimetilsilil)metil-7-octenal | 123453-92-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 6-acetoxi-7-(trimetilsilil)metil-7-octenal
• CAS: 123453-92-9
• 化学式: C₁₄H₂₆O₃Si
• 分子量: 270.444
• InChiKey: CYDQGDVXSIOLAT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.57
• 重原子数：
  18.0
• 可旋转键数：
  9.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  43.37
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  6-acetoxi-7-(trimetilsilil)metil-7-octenal 在 哌啶 、 咪唑 、 4-二甲氨基吡啶 作用下， 以 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 3.0h， 生成 (E)-1-(phenylsulfonyl)-3-<(tert-butyldimethylsilyl)oxy>-7-acetoxy-8-<(trimethylsilyl)methyl>-1,8-nonadiene
  参考文献：
  名称：

  Intramolecular palladium-catalyzed trimethylenemethane cycloadditions: initial studies

  摘要：

  The potential application of [3 + 2] cycloadditions to polycarbocycle construction is considerably enhanced by the ability to perform such reactions intramolecularly. The feasibility of such processes is explored in the context of Pd-catalyzed cycloadditions of 2-[(trimethylsilyl)methyl]allyl carboxylates, wherein trimethylenemethane (TMM) precursor fragment (donor) and the electron-deficient olefin (acceptor) is joined by a tether of simple methylene groups of 3, 4, 5, and 8 members. Several versatile synthetic routes to these substrates were developed. 2-Bromo-3-(trimethylsilyl)propene proves to be a key reagent for construction of the donor portion. Acceptors bearing esters, cyano groups, and especially sulfones have been examined. The diastereoselectivity of the reaction has been explored both in terms of ring juncture and the diastereofacial selectivity with respect to an oxygen substituent at the allylic position of the acceptor. Excellent cycloadditions to give the bicyclo[3.3.0] octyl and bicyclo[4.3.0]nonyl systems are observed, whereas larger rings cannot be obtained in this series. The choice of catalyst proves critical, the most useful being either tetrakis(triphenylphosphine)palladium and DPPE or, more generally, triisopropyl phosphite and palladium acetate. The first cycloaddition of a 1,1-dialkylated TMM precursor, which fails in intermolecular cases, has been observed in this intramolecular series to give a bridgehead-substituted bicycle. A rationale for the observed diastereoselectivity is presented.

  DOI：

  10.1021/ja00019a036
• 作为产物：
  描述：

  6-(tetrahydro-2H-pyranyloxy)hexan-1-ol 在 sodium acetate 、 对甲苯磺酸 、 magnesium 、 三乙胺 、 pyridinium chlorochromate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 6.5h， 生成 6-acetoxi-7-(trimetilsilil)metil-7-octenal
  参考文献：
  名称：

  Thomas, A. E.; Jenkins, P. R.; Robinson, G., Anales de Quimica, 1995, vol. 91, # 3-4, p. 206 - 213

  摘要：

  DOI：

文献信息

• Intramolecular palladium-catalyzed trimethylenemethane cycloadditions: initial studies
  作者：Barry M. Trost、Timothy A. Grese、Dominic M. T. Chan

  DOI：10.1021/ja00019a036

  日期：1991.9

  The potential application of [3 + 2] cycloadditions to polycarbocycle construction is considerably enhanced by the ability to perform such reactions intramolecularly. The feasibility of such processes is explored in the context of Pd-catalyzed cycloadditions of 2-[(trimethylsilyl)methyl]allyl carboxylates, wherein trimethylenemethane (TMM) precursor fragment (donor) and the electron-deficient olefin (acceptor) is joined by a tether of simple methylene groups of 3, 4, 5, and 8 members. Several versatile synthetic routes to these substrates were developed. 2-Bromo-3-(trimethylsilyl)propene proves to be a key reagent for construction of the donor portion. Acceptors bearing esters, cyano groups, and especially sulfones have been examined. The diastereoselectivity of the reaction has been explored both in terms of ring juncture and the diastereofacial selectivity with respect to an oxygen substituent at the allylic position of the acceptor. Excellent cycloadditions to give the bicyclo[3.3.0] octyl and bicyclo[4.3.0]nonyl systems are observed, whereas larger rings cannot be obtained in this series. The choice of catalyst proves critical, the most useful being either tetrakis(triphenylphosphine)palladium and DPPE or, more generally, triisopropyl phosphite and palladium acetate. The first cycloaddition of a 1,1-dialkylated TMM precursor, which fails in intermolecular cases, has been observed in this intramolecular series to give a bridgehead-substituted bicycle. A rationale for the observed diastereoselectivity is presented.
• Thomas, A. E.; Jenkins, P. R.; Robinson, G., Anales de Quimica, 1995, vol. 91, # 3-4, p. 206 - 213
  作者：Thomas, A. E.、Jenkins, P. R.、Robinson, G.、Simons, C.、Alguacil, R.、Tapia, R. A.

  DOI：——

  日期：——