(1S,4R)-4-<1-((triisopropylsiloxy)methyl)-3-tert-butoxy-1(E)-propenyl>-2-cyclopentenol | 164106-60-9

• 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: (1S,4R)-4-<1-((triisopropylsiloxy)methyl)-3-tert-butoxy-1(E)-propenyl>-2-cyclopentenol
• CAS: 164106-60-9
• 化学式: C₂₂H₄₂O₃Si
• 分子量: 382.659
• InChiKey: VXVQNEYRKYZMBW-LDMHUSQKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.86
• 重原子数：
  26.0
• 可旋转键数：
  9.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  38.69
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  (1S,4R)-4-<1-((triisopropylsiloxy)methyl)-3-tert-butoxy-1(E)-propenyl>-2-cyclopentenol 在 chromium(VI) oxide 、 硫酸 、 L-Selectride 作用下， 以 水 、 丙酮 为溶剂， 反应 4.5h， 生成 (4S)-1-<((trifluoromethyl)sulfonyl)oxy>-4-<1-((triisopropylsiloxy)methyl)-3-tert-butoxy-1(E)-propenyl>-1-cyclopentene
  参考文献：
  名称：

  Asymmetric Total Syntheses of (-)- and (+)-Strychnine and the Wieland-Gumlich Aldehyde

  摘要：

  The first asymmetric total syntheses of (-)-strychnine, ent-strychnine, and the Wieland-Gumlich aldehyde are described with full experimental details. The total synthesis of (-)-strychnine was realized in 24 steps and 3% overall yield from (1R,4S)-(+)-4-hydroxy-2-cyclopentenyl acetate (28). This synthesis fully controls the six stereogenic centers and forms the C(20) double bond of (-)-strychnine with high diastereoselection (>20:1). In the first stage of the synthesis, the (R)-cyclopentenylstannane 8 is prepared in nine steps and 30% overall yield (40% with one recycle of 38) as summarized in Scheme 4. Palladium-catalyzed carbonylative coupling of 8 with the 2-iodoaniline derivative 7 provides enone 6, which is converted to the 2-azabicyclo[3.2.1]octane 5 in seven additional steps. This latter sequence proceeds in 36% overall yield (Scheme 6). The central step of the total synthesis is aza-Cope-Mannich rearrangement of 5 which proceeds in 98% yield to form the pentacyclic intermediate 4 (Scheme 7). In five additional steps 4 is converted to the Wieland-Gumlich aldehyde 2, which is the ultimate precursor of (-)strychnine. A slight modification of this synthesis strategy allowed ent-strychnine to be prepared and provided the first samples of this unnatural enantiomer for pharmacological studies (Scheme 8). The efficiency and conciseness of this synthesis provide an important benchmark of the power of the aza-Cope rearrangement-Mannich reaction to solve formidable problems in alkaloid construction.

  DOI：

  10.1021/ja00126a017
• 作为产物：
  描述：

  三异丙基氯硅烷 、 4-tert-butoxy-2-<(1R,4S)-4-hydroxy-2-cyclopentenyl>-2(E)-buten-1-ol 在 1,1,2,3-四甲基胍 作用下， 以 various solvent(s) 为溶剂， 反应 8.0h， 生成 (1S,4R)-4-<1-((triisopropylsiloxy)methyl)-3-tert-butoxy-1(E)-propenyl>-2-cyclopentenol 、 (3R,5S)-3-((E)-3-tert-Butoxy-1-triisopropylsilanyloxymethyl-propenyl)-5-triisopropylsilanyloxy-cyclopentene
  参考文献：
  名称：

  Asymmetric Total Syntheses of (-)- and (+)-Strychnine and the Wieland-Gumlich Aldehyde

  摘要：

  The first asymmetric total syntheses of (-)-strychnine, ent-strychnine, and the Wieland-Gumlich aldehyde are described with full experimental details. The total synthesis of (-)-strychnine was realized in 24 steps and 3% overall yield from (1R,4S)-(+)-4-hydroxy-2-cyclopentenyl acetate (28). This synthesis fully controls the six stereogenic centers and forms the C(20) double bond of (-)-strychnine with high diastereoselection (>20:1). In the first stage of the synthesis, the (R)-cyclopentenylstannane 8 is prepared in nine steps and 30% overall yield (40% with one recycle of 38) as summarized in Scheme 4. Palladium-catalyzed carbonylative coupling of 8 with the 2-iodoaniline derivative 7 provides enone 6, which is converted to the 2-azabicyclo[3.2.1]octane 5 in seven additional steps. This latter sequence proceeds in 36% overall yield (Scheme 6). The central step of the total synthesis is aza-Cope-Mannich rearrangement of 5 which proceeds in 98% yield to form the pentacyclic intermediate 4 (Scheme 7). In five additional steps 4 is converted to the Wieland-Gumlich aldehyde 2, which is the ultimate precursor of (-)strychnine. A slight modification of this synthesis strategy allowed ent-strychnine to be prepared and provided the first samples of this unnatural enantiomer for pharmacological studies (Scheme 8). The efficiency and conciseness of this synthesis provide an important benchmark of the power of the aza-Cope rearrangement-Mannich reaction to solve formidable problems in alkaloid construction.

  DOI：

  10.1021/ja00126a017