(R)-4-methyl-2-trimethylsilyloxypentanenitrile | 497099-91-9

• 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: (R)-4-methyl-2-trimethylsilyloxypentanenitrile
• 英文别名: (2R)-4-methyl-2-trimethylsilyloxypentanenitrile
• CAS: 497099-91-9
• 化学式: C₉H₁₉NOSi
• 分子量: 185.341
• InChiKey: KNQADDZAKRMGAT-SECBINFHSA-N

物化性质

• 沸点：
  202.8±23.0 °C(Predicted)
• 密度：
  0.868±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.78
• 重原子数：
  12
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  33
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (R)-4-methyl-2-trimethylsilyloxypentanenitrile 在 盐酸 作用下， 以 乙醚 为溶剂， 反应 2.0h， 生成 (R)-2-hydroxy-4-methylpentanenitrile
  参考文献：
  名称：

  双功能BINOL配体的合成及其在羰基化合物不对称加成中的应用

  摘要：

  分别从BINOL和H 8 BINOL与吗啉代甲醇的反应中开发了双功能BINOL和H 8 BINOL配体（S）-6和（S）-8的高效一步合成方法。这些化合物的X射线分析表明它们在结构上有相似之处和不同之处。双功能H 8 BINOL（S）-8已发现对二苯基锌与许多脂族和芳族醛的反应具有很高的对映选择性，尤其是对于线性脂族醛而言，对映选择性最强的催化剂。与开发用于添加二苯锌的其他催化剂不同，该催化剂通常需要在冷却（或加热）的同时添加大量的二乙基锌以实现高对映选择性，使用（S）-8无需添加剂，在室温下可获得优异的结果温度。（S）-8与二乙基锌和Ti（O i Pr）4结合可以催化高度对映选择性的苯乙炔加成芳族醛。尽管对映选择性还不是很高，但它在室温下还可以促进苯乙炔向苯乙酮的添加。在不使用Ti（O i Pr）4和路易斯碱添加剂的情况下，（S）-8与二乙基锌结合可以催化丙酸甲酯与醛的反应，形成高官能度

  DOI：

  10.1016/j.tet.2006.06.049
• 作为产物：
  描述：

  异戊醛 在 吡啶 、 (R)-hydroxynitrile lyase 作用下， 以 水 为溶剂， 生成 (R)-4-methyl-2-trimethylsilyloxypentanenitrile
  参考文献：
  名称：

  Stereoselective synthesis of β-amino-γ-butyrolactones

  摘要：

  A novel synthesis of optically active beta-amino-gamma-butyrolactones is described. O-Silylated (R)-cyanohydrins (R)-3 (derived from aldehydes 1 by (R)-hydroxynitrile lyase ((R)-PaHNL)-catalyzed addition of HCN) were reacted with allyl Grignard to give amino alcohols (4R,5S)-5 after reduction. In the addition of crotyl Grignard reagent, workup conditions are decisive for the formation of amino alcohol 8, which was isolated Lis a diastercoisomeric mixture the acetylated main diastereoisomer (3S,4R,5R)-10 was separated. Ozonolysis of the acetylated amino alcohols (4S,5R)-7a,b and (3S,4S,5R)-10 affords the aldehydes 12a-c, which were directly oxidized with CrO3 in dilute H2SO4 to yield the beta-acetamido-gamma-acetoxycarboxylic acids (3S,4R)-13a,b and (2R,3S,4R)-13c. Compounds 13 cyclized spontaneously Under acidic conditions to afford beta-acetamido-gamma-butyrolactones (4S,5R)-14a,b and (3R,4S,5R)-14c. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(02)00437-8

文献信息

• Asymmetric addition of trimethylsilyl cyanide to aldehydes promoted by chiral polymeric vanadium(V) salen complex as an efficient and recyclable catalyst
  作者：Noor-ul H. Khan、Santosh Agrawal、Rukhsana I. Kureshy、Sayed H.R. Abdi、Vishal J. Mayani、Raksh V. Jasra

  DOI：10.1016/j.tetasy.2006.09.024

  日期：2006.10

  The asymmetric addition of trimethylsilyl cyanide to various aldehydes catalyzed by efficient new vanadyl polymeric salen complexes having 12 repeating salen units was investigated at room temperature. An excellent yield of the trimethylsilylether of cyanohydrins (up to 98%) with high chiral induction (96%) in case of 2-methylbenzaldehyde was achieved in 18 h. The catalyst recovered four times with

  在室温下研究了由具有12个重复的salen单元的有效的新的钒基聚合物salen配合物催化的三甲基甲硅烷基氰化物向各种醛的不对称加成。在2-甲基苯甲醛的情况下，在18小时内获得了出色的氰醇三甲基甲硅烷基醚收率（高达98％）和高手性诱导率（96％）。该催化剂在保持其性能的情况下回收了四次。
• Synthesis of the bifunctional BINOL ligands and their applications in the asymmetric additions to carbonyl compounds
  作者：Ying-Chuan Qin、Lan Liu、Michal Sabat、Lin Pu

  DOI：10.1016/j.tet.2006.06.049

  日期：2006.10

  the diphenylzinc addition which often require the addition of a significant amount of diethylzinc with cooling (or heating) the reaction mixture in order to achieve high enantioselectivity, using (S)-8 needs no additive and gives excellent results at room temperature. (S)-8 in combination with diethylzinc and Ti(OiPr)4 can catalyze the highly enantioselective phenylacetylene addition to aromatic aldehydes

  分别从BINOL和H 8 BINOL与吗啉代甲醇的反应中开发了双功能BINOL和H 8 BINOL配体（S）-6和（S）-8的高效一步合成方法。这些化合物的X射线分析表明它们在结构上有相似之处和不同之处。双功能H 8 BINOL（S）-8已发现对二苯基锌与许多脂族和芳族醛的反应具有很高的对映选择性，尤其是对于线性脂族醛而言，对映选择性最强的催化剂。与开发用于添加二苯锌的其他催化剂不同，该催化剂通常需要在冷却（或加热）的同时添加大量的二乙基锌以实现高对映选择性，使用（S）-8无需添加剂，在室温下可获得优异的结果温度。（S）-8与二乙基锌和Ti（O i Pr）4结合可以催化高度对映选择性的苯乙炔加成芳族醛。尽管对映选择性还不是很高，但它在室温下还可以促进苯乙炔向苯乙酮的添加。在不使用Ti（O i Pr）4和路易斯碱添加剂的情况下，（S）-8与二乙基锌结合可以催化丙酸甲酯与醛的反应，形成高官能度
• Stereoselective synthesis of β-amino-γ-butyrolactones
  作者：Jürgen Roos、Franz Effenberger

  DOI：10.1016/s0957-4166(02)00437-8

  日期：2002.9

  A novel synthesis of optically active beta-amino-gamma-butyrolactones is described. O-Silylated (R)-cyanohydrins (R)-3 (derived from aldehydes 1 by (R)-hydroxynitrile lyase ((R)-PaHNL)-catalyzed addition of HCN) were reacted with allyl Grignard to give amino alcohols (4R,5S)-5 after reduction. In the addition of crotyl Grignard reagent, workup conditions are decisive for the formation of amino alcohol 8, which was isolated Lis a diastercoisomeric mixture the acetylated main diastereoisomer (3S,4R,5R)-10 was separated. Ozonolysis of the acetylated amino alcohols (4S,5R)-7a,b and (3S,4S,5R)-10 affords the aldehydes 12a-c, which were directly oxidized with CrO3 in dilute H2SO4 to yield the beta-acetamido-gamma-acetoxycarboxylic acids (3S,4R)-13a,b and (2R,3S,4R)-13c. Compounds 13 cyclized spontaneously Under acidic conditions to afford beta-acetamido-gamma-butyrolactones (4S,5R)-14a,b and (3R,4S,5R)-14c. (C) 2002 Elsevier Science Ltd. All rights reserved.