2-methyl-2-(trimethylsilyloxy)heptanenitrile

• 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: 2-methyl-2-(trimethylsilyloxy)heptanenitrile
• 英文别名: 2-trimethylsilyloxy-2-methylheptanenitrile；(R)-2-trimethylsilyloxy-2-methylheptanenitrile；(R)-2-methyl-2-trimethylsilyloxyheptanenitrile；(2R)-2-methyl-2-trimethylsilyloxyheptanenitrile
• 化学式: C₁₁H₂₃NOSi
• 分子量: 213.395
• InChiKey: SZVSNHBZDHGWOW-LLVKDONJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  14
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  33
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  2-庚酮 、 三甲基氰硅烷 在 titanium(IV) isopropylate 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 36.0h， 生成 (S)-2-methyl-2-trimethylsilyloxyheptanenitrile 、 2-methyl-2-(trimethylsilyloxy)heptanenitrile
  参考文献：
  名称：

  双功能Ti（IV）配合物催化的酮的高度对映选择性氰基硅烷化

  摘要：

  由（S）-脯氨酰胺（2a），异丙醇钛（IV）和酚式N-氧化物（3f）组成的双功能催化剂体系在酮的对映选择性氰基硅烷化反应中显示出高催化效率。在2.5mol％催化剂的存在下，多种芳族和脂族酮以优异的产率（高达96％）和高的对映选择性（高达96％ee）被转化为相应的叔氰醇O -TMS醚。说明了拟议的催化循环，以解释不对称感应的起源。

  DOI：

  10.1016/j.tet.2007.10.093

文献信息

• Catalytic enantioselective cyanosilylation of ketones: improvement of enantioselectivity and catalyst turn-over by ligand tuning
  作者：Yoshitaka Hamashima、Motomu Kanai、Masakatsu Shibasaki

  DOI：10.1016/s0040-4039(00)02039-6

  日期：2001.1

  the bifunctional catalyst 1 afforded the improved catalyst 2, which promoted the cyanosilylation of ketones with higher enantioselectivity as well as with improved catalyst turn-over with a factor of up to 10. Thus, chiral quaternary α-hydroxynitriles were obtained with excellent ee (up to 94% ee) using 1 mol% of 2 in the case of aryl ketones and 2.5 mol% of 2 in the case of aliphatic ketones.

  对双官能催化剂1进行立体和电子调谐，得到了改进的催化剂2，该催化剂以较高的对映选择性和最大为10的改进的催化剂周转率促进了酮的氰基甲硅烷基化反应。在芳基酮的情况下使用1 mol％的2和在脂族酮的情况下使用2.5 mol％的2时，具有优异的ee（最高94％ee）。
• Effective Activation of the Chiral Salen/Ti(OiPr)4 Catalyst with Achiral PhenolicN-Oxides as Additives in the Enantioselective Cyanosilylation of Ketones
  作者：Bin He、Fu-Xue Chen、Yan Li、Xiaoming Feng、Guolin Zhang

  DOI：10.1002/ejoc.200400411

  日期：2004.11

  the asymmetric cyanosilylation of ketones. By using 10 mol % of chiral salen-titanium(IV) complex in combination with 1 mol% achiral phenolic N-oxide as an additive, aromatic, aliphatic and heterocyclic ketones have been converted into the corresponding cyanohydrin trimethylsilyl ethers in 58-96% yields with 56-82% ee. Several factors concerning the reactivity and enantioselectivity have been discussed

  已发现手性钛 (IV) 配合物与酚类 N 氧化物添加剂的活化为酮的不对称氰基硅烷化提供了一种替代策略。通过使用 10 mol% 的手性 salen-titanium (IV) 配合物与 1 mol% 的非手性酚 N-氧化物作为添加剂，芳香族、脂肪族和杂环酮以 58-96% 的产率转化为相应的氰醇三甲基甲硅烷基醚含 56-82% ee。已经讨论了有关反应性和对映选择性的几个因素。已经提出了基于实验现象和研究的催化循环来解释这种活化和不对称诱导的起源。
• Asymmetric cyanosilylation of ketones catalyzed by novel chiral N,N′-dioxide titanium complexes
  作者：Qinghan Li、Xiaohua Liu、Jun Wang、Ke Shen、Xiaoming Feng

  DOI：10.1016/j.tetlet.2006.04.003

  日期：2006.6

  A novel C2-symmetric chiral N,N′-dioxide titanium complex was described, which could efficiently catalyze the asymmetric cyanosilylation of ketones in high yields with up to 92% ee under mild conditions. In addition, the catalyst system was simple and the ligands could be easily prepared from commercially available chiral amino acid.

  描述了一种新型的C 2对称手性N，N'-二氧化钛钛配合物，该配合物在温和条件下可高效催化酮的不对称氰基硅烷化反应，收率高达92％ee。另外，该催化剂体系简单，并且可以容易地从市售手性氨基酸制备配体。
• Enantioselective Cyanosilylation of Ketones with Amino Acid/BINAP/Ruthenium(II)-Lithium Phenoxide Catalyst Systems
  作者：Masato Uemura、Nobuhito Kurono、Yusuke Sakai、Takeshi Ohkuma

  DOI：10.1002/adsc.201200027

  日期：2012.7.9

  Enantioselective reactions of simple ketones, α,α‐ and β,β‐dialkoxy ketones, and α‐alkoxy ketones with trimethylsilyl cyanide catalyzed by the bimetallic systems of amino acid/BINAP/ruthenium(II) complexes and lithium phenoxide have been studied [BINAP=2,2′‐bis(diphenylphosphino)‐1,1′‐binaphthyl]. The Ru(PhGly)2(BINAP)‐lithium phenoxide system showed high enantioselectivity for the reaction of acetophenone

  研究了简单的酮，α，α和β，β-二烷氧基酮和α-烷氧基酮与氨基酸/ BINAP /钌（II）配合物和二氧化锂的双金属体系催化的三甲基甲硅烷基氰化物的对映选择性反应[BINAP = 2,2'-双（二苯基膦基）-1,1'-联萘基]。Ru（PhGly）2（BINAP）-苯酚锂体系对苯乙酮衍生物的反应具有很高的对映选择性，从而可以提供高达90％ee的氰化产物[PhGly =苯基甘氨酸]。对于二烷氧基酮和α-烷氧基酮的氰基硅烷化反应，Ru（t -Leu ）2（BINAP）-苯酚氧化锂系统表现出最佳的催化剂性能，可生产ee高达99％ee和98％的氰醇衍生物ee分别[ t -Leu =叔亮氨酸]。在最佳情况下，出色的催化活性导致反应完全转化，底物与催化剂的摩尔比（S / C）为10,000。
• Cooperative Catalysis by Tertiary Amino-Thioureas:  Mechanism and Basis for Enantioselectivity of Ketone Cyanosilylation
  作者：Stephan J. Zuend、Eric N. Jacobsen

  DOI：10.1021/ja0735352

  日期：2007.12.1

  The mechanism of the enantioselective cyanosilylation of ketones catalyzed by tertiary aminothiourea derivatives was investigated using a combination of experimental and theoretical methods. The kinetic analysis is consistent with a cooperative mechanism in which both the thiourea and the tertiary amine of the catalyst are involved productively in the rate-limiting cyanide addition step. Density functional theory calculations were used to distinguish between mechanisms involving thiourea activation of ketone or of cyanide in the enantioselectivity-determining step. The strong correlation obtained between experimental and calculated ee's for a range of substrates and catalysts provides support for the most favorable calculated transition structures involving amine-bound HCN adding to thiourea-bound ketone. The calculations suggest that enantioselectivity arises from direct interactions between the ketone substrate and the amino-acid derived portion of the catalyst. On the basis of this insight, more enantioselective catalysts with broader substrate scope were prepared and evaluated experimentally.