4,4-dimethyl-3-tris(trimethylsilyl)siloxypentanal | 875288-44-1

• 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: 4,4-dimethyl-3-tris(trimethylsilyl)siloxypentanal
• 英文别名: 4,4-Dimethyl-3-tris(trimethylsilyl)silyloxypentanal；4,4-dimethyl-3-tris(trimethylsilyl)silyloxypentanal
• CAS: 875288-44-1
• 化学式: C₁₆H₄₀O₂Si₄
• 分子量: 376.834
• InChiKey: KENOKYBWNAIYCC-UHFFFAOYSA-N

物化性质

• 沸点：
  341.9±44.0 °C(Predicted)
• 密度：
  0.857±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  22
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.94
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  异丙烯氧基三(三甲基硅烷基)硅烷 、 4,4-dimethyl-3-tris(trimethylsilyl)siloxypentanal 在 双三氟甲烷磺酰亚胺 作用下， 以 二氯甲烷 为溶剂， 以68%的产率得到
  参考文献：
  名称：

  控制立体化学在聚酮化合物合成：1,3-与1,2-不对称诱导在甲基酮醇醛增补β超甲硅烷氧基醛†

  摘要：

  描述了将甲基酮醛醇缩合至β-甲硅烷氧基和α-甲基β-甲硅烷氧基醛。仔细控制机械上不同的羟醛反应可利用1,2-和1,3-不对称诱导，选择性地形成顺式和反式羟醛加合物，并具有出色的非对映控制性。实验和理论研究为控制非对映选择性的因素提供了见识。

  DOI：

  10.1039/c3sc51183a
• 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 3.25h， 生成 4,4-dimethyl-3-tris(trimethylsilyl)siloxypentanal
  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

• “Super Silyl” Group for Diastereoselective Sequential Reactions:  Access to Complex Chiral Architecture in One Pot
  作者：Matthew B. Boxer、Hisashi Yamamoto

  DOI：10.1021/ja0693542

  日期：2007.3.1

  We have shown that the tris(trimethylsilyl)silyl (TTMSS) silyl enol ether of acetaldehyde undergoes aldehyde cross-aldol reactions with high selectivity and the extremely low catalyst loading (0.05 mol % of HNTf2) allows for one-pot sequential reactions where acidic or basic nucleophiles can be subsequently added. Various ketone-derived silyl enol ethers, Grignard reagents, and dienes succeeded, generating relatively complex molecular architectures in a single step. This represents the first case where, in a single pot, highly acidic conditions followed by very basic conditions were tolerated to give products with high diastereoselectivities and good yields.
• Controlling stereochemistry in polyketide synthesis: 1,3- vs. 1,2-asymmetric induction in methyl ketone aldol additions to β-super siloxy aldehydes
  作者：Patrick B. Brady、Brian J. Albert、Matsujiro Akakura、Hisashi Yamamoto

  DOI：10.1039/c3sc51183a

  日期：——

  The aldol addition of methyl ketones to β-siloxy and α-methyl β-siloxy aldehydes is described. Careful control of mechanistically distinct aldol reactions leverages 1,2- and 1,3-asymmetric induction, selectively forming syn and anti aldol adducts with excellent diastereocontrol. Experimental and theoretical investigations have provided insight to the factors governing diastereoselectivity.

  描述了将甲基酮醛醇缩合至β-甲硅烷氧基和α-甲基β-甲硅烷氧基醛。仔细控制机械上不同的羟醛反应可利用1,2-和1,3-不对称诱导，选择性地形成顺式和反式羟醛加合物，并具有出色的非对映控制性。实验和理论研究为控制非对映选择性的因素提供了见识。
• 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.