6,6-dimethyl-3,5-bis-tris(trimethylsilyl)siloxyheptanal

• 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: 6,6-dimethyl-3,5-bis-tris(trimethylsilyl)siloxyheptanal
• 英文别名: (3S,5R)-6,6-dimethyl-3,5-bis[tris(trimethylsilyl)silyloxy]heptanal
• 化学式: C₂₇H₇₀O₃Si₈
• 分子量: 667.535
• InChiKey: INJVZVPXLDRRPI-CLJLJLNGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.17
• 重原子数：
  38
• 可旋转键数：
  15
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.96
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  6,6-dimethyl-3,5-bis-tris(trimethylsilyl)siloxyheptanal 、 4-甲氧苯磺酰肼 以 甲醇 为溶剂， 反应 0.5h， 以86%的产率得到
  参考文献：
  名称：

  Tris(trimethylsilyl)silyl-Governed Aldehyde Cross-Aldol Cascade Reaction

  摘要：

  The use of the tris(trimethylsilyl)silyl (TTMSS) group in aldehyde-derived silyl enol ethers affords aldehyde cross-aldol products with high yields and allows for unprecedented reactivity. The reaction is catalyzed by 0.05 mol % of HNTf2, and can easily be managed to give beta,delta-bis-, beta,delta,gamma-tris-, and beta,delta,zeta-tris-hydroxy-aldehydes with extremely high selectivity by simple stoichiometric control. High diastereoselectivity is obtained in all cases, and the use of chiral aldehydes affords Felkin products when there are nonchelating substituents, chelation products when there is a chelating sbustituent, and syn products when there is beta-substitution. HNTf2 is proposed to be an initiator, and highly Lewis acidic TTMSSNTf2 is the true catalyst.

  DOI：

  10.1021/ja054725k
• 作为产物：
  描述：

  三(三甲基硅基)硅烷 在 三氟甲磺酸 、 双三氟甲烷磺酰亚胺 作用下， 以 二氯甲烷 为溶剂， 反应 4.0h， 生成 6,6-dimethyl-3,5-bis-tris(trimethylsilyl)siloxyheptanal
  参考文献：
  名称：

  Tris(trimethylsilyl)silyl-Governed Aldehyde Cross-Aldol Cascade Reaction

  摘要：

  The use of the tris(trimethylsilyl)silyl (TTMSS) group in aldehyde-derived silyl enol ethers affords aldehyde cross-aldol products with high yields and allows for unprecedented reactivity. The reaction is catalyzed by 0.05 mol % of HNTf2, and can easily be managed to give beta,delta-bis-, beta,delta,gamma-tris-, and beta,delta,zeta-tris-hydroxy-aldehydes with extremely high selectivity by simple stoichiometric control. High diastereoselectivity is obtained in all cases, and the use of chiral aldehydes affords Felkin products when there are nonchelating substituents, chelation products when there is a chelating sbustituent, and syn products when there is beta-substitution. HNTf2 is proposed to be an initiator, and highly Lewis acidic TTMSSNTf2 is the true catalyst.

  DOI：

  10.1021/ja054725k

文献信息

• Tris(trimethylsilyl)silyl-Governed Aldehyde Cross-Aldol Cascade Reaction
  作者：Matthew B. Boxer、Hisashi Yamamoto

  DOI：10.1021/ja054725k

  日期：2006.1.1

  The use of the tris(trimethylsilyl)silyl (TTMSS) group in aldehyde-derived silyl enol ethers affords aldehyde cross-aldol products with high yields and allows for unprecedented reactivity. The reaction is catalyzed by 0.05 mol % of HNTf2, and can easily be managed to give beta,delta-bis-, beta,delta,gamma-tris-, and beta,delta,zeta-tris-hydroxy-aldehydes with extremely high selectivity by simple stoichiometric control. High diastereoselectivity is obtained in all cases, and the use of chiral aldehydes affords Felkin products when there are nonchelating substituents, chelation products when there is a chelating sbustituent, and syn products when there is beta-substitution. HNTf2 is proposed to be an initiator, and highly Lewis acidic TTMSSNTf2 is the true catalyst.