(1R*,9R*)-9-cyano-7-methylene-2-<(tert-butyldimethylsilyl)oxy>bicyclo<4.3.0>nonane | 136277-23-1

• 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*,9R*)-9-cyano-7-methylene-2-<(tert-butyldimethylsilyl)oxy>bicyclo<4.3.0>nonane
• 英文别名: (1R^*,9R^*)-9-cyano-7-methylene-2-<(tert-butyldimethylsilyl)oxy>bicyclo<4.3.0>nonane；(1R^*,9R^*)-9-cyano-7-methylene-2-[(tert-butyldimethylsilyl)oxy]bicyclo[4.3.0]nonane
• CAS: 136277-23-1；136277-25-3；136277-27-5；136277-28-6；136277-30-0
• 化学式: C₁₇H₂₉NOSi
• 分子量: 291.509
• InChiKey: ADITVMBDBAHTLA-QKPAOTATSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.89
• 重原子数：
  20.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  33.02
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (1R*,9R*)-9-cyano-7-methylene-2-<(tert-butyldimethylsilyl)oxy>bicyclo<4.3.0>nonane 在 Celite 、 四丁基氟化铵 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 14.0h， 生成 (1R^*,6S^*,9R^*)-9-cyano-7-methylene-2-oxobicyclo<4.3.0>nonane
  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：

  1,6-己二醇 在 哌啶 、 咪唑 、 4-二甲氨基吡啶 、 四(三苯基膦)钯 、 N,O-双三甲硅基乙酰胺 、 草酰氯 、 Celite 、 水 、 四丁基碘化铵 、 potassium hydride 、 二甲基亚砜 、 pyridinium chlorochromate 、 2,3-二氯-5,6-二氰基-1,4-苯醌 、 1,2-双(二苯基膦)乙烷 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 18.17h， 生成 (1R*,9R*)-9-cyano-7-methylene-2-<(tert-butyldimethylsilyl)oxy>bicyclo<4.3.0>nonane
  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