(S)-1-(trimethylsilyloxy)indane-1-carbonitrile

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚满类
• 英文名称: (S)-1-(trimethylsilyloxy)indane-1-carbonitrile
• 英文别名: (S)-1-trimethylsilyloxyindane-1-carbonitrile；(S)-1-((Trimethylsilyl)oxy)-2,3-dihydro-1H-indene-1-carbonitrile；(1S)-1-trimethylsilyloxy-2,3-dihydroindene-1-carbonitrile
• 化学式: C₁₃H₁₇NOSi
• 分子量: 231.37
• InChiKey: XZTOBAKJNLBBRH-CYBMUJFWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 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：

  三甲基氰硅烷 、 1-茚酮 在 titanium(IV) isopropylate (2S)-N-{(1R,2R)-2-[(S)-pyrrolidine-2-carboxamido]-1,2-diphenylethyl}pyrrolidine-2-carboxamide 作用下， 以 二氯甲烷 为溶剂， 反应 100.0h， 生成 (S)-1-(trimethylsilyloxy)indane-1-carbonitrile 、 (R)-1-(trimethylsilyloxy)indane-1-carbonitrile
  参考文献：
  名称：

  含氮双功能催化剂催化酮的对映选择性氰基硅烷化反应

  摘要：

  一种高效且旋光的双官能四氮杂配体（2 S）-N -{（1 R，2 R）-2-[（S）-吡咯烷-2-甲酰胺基] -1,2-二苯乙基}吡咯烷-2-甲酰胺已经开发出将三甲基甲硅烷基氰化物（TMSCN）添加到酮中的方法。发现基于单金属钛配合物的双官能催化剂体系是高度对映选择性的催化剂，其提供高达94％ee的O -TMS氰醇。已经提出了一种可能的过渡态来解释激活和不对称电感的起源。

  DOI：

  10.1002/adsc.200505418

文献信息

• Me₂(CH₂Cl)SiCN: Bifunctional Cyanating Reagent for the Synthesis of Tertiary Alcohols with a Chloromethyl Ketone Moiety via Ketone Cyanosilylation
  作者：Xing-Ping Zeng、Jian Zhou

  DOI：10.1021/jacs.6b05601

  日期：2016.7.20

  We report a novel bifunctional cyanating reagent, Me2(CH2Cl)SiCN, which paves the way to a one-pot sequential synthesis of tertiary alcohols featuring a chloromethyl ketone moiety via enantioselective ketone cyanosilylation. This method contributes to gram-scale enantioselective total synthesis of the aggregation pheromone of the Colorado potato beetle, (S)-CPB.

  我们报告了一种新型双功能氰化试剂 Me2(CH2Cl)SiCN，它为通过对映选择性酮氰硅烷化合成具有氯甲基酮部分的叔醇的一锅法顺序合成铺平了道路。该方法有助于科罗拉多马铃薯甲虫 (S)-CPB 聚集信息素的克级对映选择性全合成。
• 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。
• Aluminum-Catalyzed Asymmetric Addition of TMSCN to Aromatic and Aliphatic Ketones Promoted by an Easily Accessible and Recyclable Peptide Ligand
  作者：Hongbo Deng、Markus P. Isler、Marc L. Snapper、Amir H. Hoveyda

  DOI：10.1002/1521-3773(20020315)41:6<1009::aid-anie1009>3.0.co;2-f

  日期：2002.3.15
• 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.