(S)-cyano(4-trifluoromethylphenyl)methyl acetate

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (S)-cyano(4-trifluoromethylphenyl)methyl acetate
• 英文别名: (S)-(-)-1-cyano-1-[4-(trifluoromethyl)phenyl]methyl acetate；O-acetyl-2-hydroxy-2-(4-trifuloromethylphenyl)acetonitrile；(S)-(-)-acetoxy-(4-trifluoromethyl-phenyl)-acetonitrile；cyano[4-(trifluoromethyl)phenyl]methyl acetate；[(S)-cyano-[4-(trifluoromethyl)phenyl]methyl] acetate
• 化学式: C₁₁H₈F₃NO₂
• 分子量: 243.185
• InChiKey: PNTSBTAVPHHZMK-SNVBAGLBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  50.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  对三氟甲基苯甲醛 在 scandium trifluoromethanesulfonate 、 (R)-1,1'-Bi-2-naphthol 、 lithium isopropoxide 作用下， 以 甲苯 、 乙腈 为溶剂， 反应 1.33h， 生成 (S)-cyano(4-trifluoromethylphenyl)methyl acetate
  参考文献：
  名称：

  Chiral Lithium Binaphtholate Aqua Complex as a Highly Effective Asymmetric Catalyst for Cyanohydrin Synthesis

  摘要：

  A highly enantioselective cyanohydrin synthesis with aromatic aldehydes using chiral lithium binaphtholate aqua or alcohol complexes has been developed and is a simple and inexpensive catalyst suitable for process chemistry to give gram-scale cyanohydrins successfully. Dramatic improvements in enantiomeric excess have been realized along with an interesting changeover in absolute stereochemistry of cyanohydrin product against the thoroughly "dry" catalytic systems.

  DOI：

  10.1021/ja051125c

文献信息

• Kinetics and mechanism of vanadium catalysed asymmetric cyanohydrin synthesis in propylene carbonate
  作者：Michael North、Marta Omedes-Pujol

  DOI：10.3762/bjoc.6.119

  日期：——

  Propylene carbonate can be used as a green solvent for the asymmetric synthesis of cyanohydrin trimethylsilyl ethers from aldehydes and trimethylsilyl cyanide catalysed by VO(salen)NCS, though reactions are slower in this solvent than the corresponding reactions carried out in dichloromethane. A mechanistic study has been undertaken, comparing the catalytic activity of VO(salen)NCS in propylene carbonate

  碳酸丙烯酯可用作绿色溶剂，用于在 VO(salen)NCS 的催化下由醛和三甲基氰基氰化物不对称合成氰醇三甲基甲硅烷基醚，尽管在该溶剂中的反应比在二氯甲烷中进行的相应反应慢。已经进行了一项机理研究，比较了 VO(salen)NCS 在碳酸亚丙酯和二氯甲烷中的催化活性。在两种溶剂中的反应都遵循整体二级动力学，反应速率取决于醛和三甲基氰化甲硅烷的浓度。确定了关于 VO(salen)NCS 的顺序，发现从二氯甲烷中的 1.2 减少到碳酸丙烯酯中的 1.0，表明在碳酸丙烯酯中，VO(salen)NCS 仅作为单核物质存在，而在二氯甲烷中存在双核物质，它们先前已被证明是造成大部分催化活性的原因。来自 (5)(1)V NMR 光谱的证据表明，碳酸丙烯酯与 VO(salen)NCS 配位，阻断了自由配位位点，从而抑制了其路易斯酸度并解释了催化活性的降低。这一解释得到了哈米特分析研究的进一步支持，该研究表明路易斯碱催化对碳酸亚丙酯中
• Process for the cyanation of aldehydes
  申请人：NESMEY ANOV INSTITUTE OF ORGANOELEMENT COMPOUNDS

  公开号：US20030199706A1

  公开（公告）日：2003-10-23

  A process for cyanating an aldehyde is provided. The process comprises reacting the aldehyde with: i) a cyanide source which does not comprise a Si—CN bond or a C—(C═O)—CN moiety; and ii) a substrate susceptible to nucleophilic attack not comprising a halogen leaving group; in the presence of a chiral catalyst. Preferably, the chiral catalyst is a chiral vanadium or titanium catalyst. The cyanide source is preferably an alkali metal cyanide and the substrate susceptible to nucleophilic attack not comprising a halogen leaving group is a carboxylic anhydride.

  提供一种氰化醛的方法。该方法包括将醛与：i) 不包括Si—CN键或C—(C═O)—CN基团的氰源反应；和ii) 一种易受亲核攻击的底物，不包括卤素离去基团；在手性催化剂的存在下反应。最好的手性催化剂是手性钒或钛催化剂。氰源最好是碱金属氰化物，易受亲核攻击的底物不包括卤素离去基团是羧酸酐。
• Catalytic Asymmetric Synthesis of O-Acetylcyanohydrins from Potassium Cyanide, Acetic Anhydride, and Aldehydes, Promoted by Chiral Salen Complexes of Titanium(IV) and Vanadium(V)
  作者：Yuri N. Belokon、Paola Carta、Andrey V. Gutnov、Viktor Maleev、Margarita A. Moskalenko、Lidia V. Yashkina、Nicolai S. Ikonnikov、Nikolai V. Voskoboev、Viktor N. Khrustalev、Michael North

  DOI：10.1002/1522-2675(200210)85:10<3301::aid-hlca3301>3.0.co;2-2

  日期：2002.10

  The utility of the chiral [Ti(μ-O)(salen)]2 complexes (R)- and (S)-1 (H2salen was prepared from (R,R)- or (S,S)-cyclohexane-1,2-diamine and 3,5-di(tert-butyl)-2-hydroxybenzaldehyde) as catalysts for the asymmetric addition of KCN and Ac2O to aldehydes to produce O-acetylcyanohydrins was investigated. It was shown that the complexes were active at a substrate/catalyst ratio of 100 : 1 and produced the

  手性 [Ti(μ-O)(salen)]2 配合物 (R)- 和 (S)-1 (H2salen 由 (R,R)- 或 (S,S)-cyclohexane-1 制备,研究了 2-二胺和 3,5-二（叔丁基）-2-羟基苯甲醛）作为催化剂，将 KCN 和 Ac2O 不对称加成到醛中以生产 O-乙酰氰醇。结果表明，该配合物在底物/催化剂比率为 100:1 时具有活性，并在 -40° 时产生 ee 在 60-92% 范围内的 O-保护氰醇。其他配合物 [Ti2(AcO)2(μ-O)(salen)2] ((R)-4) 和 [Ti(CF3COO)2(salen)] ((R)-5) 由 (R) 制备)-1 用不同量的Ac2O 和(CF3CO)2O 处理，并在相同条件下测试它们的催化活性。发现(R)-4 的效率甚至高于(R)-1，而(R)-5 是无活性的。VIV和VV的相应Salen配合物的合成，[V(O)(salen)]
• Asymmetric catalysis of carbon–carbon bond forming reactions using amino acid-derived C1-symmetrical salen ligands
  作者：Yuri N. Belokon′、Jamie Hunt、Michael North

  DOI：10.1016/j.tetasy.2008.11.037

  日期：2008.12

  Four amino acids (alanine, valine, phenylalanine and phenylglycine) have been converted into C1-symmetrical salen ligands and complexed to titanium, vanadium, copper and cobalt. The resulting complexes have been used as asymmetric catalysts for asymmetric cyanohydrin synthesis, asymmetric Strecker reactions, asymmetric synthesis of α-methyl amino acids and asymmetric Darzens condensations. Satisfactory

  四种氨基酸（丙氨酸，缬氨酸，苯丙氨酸和苯甘氨酸）已转化为C 1对称的salen配体，并与钛，钒，铜和钴络合。所得的络合物已用作不对称的催化剂，用于不对称的氰醇合成，不对称的Strecker反应，α-甲基氨基酸的不对称合成和不对称的Darzens缩合。从（salen）金属配合物用作手性路易斯酸的反应中获得了令人满意的不对称诱导水平，但是从在固液相转移条件下进行的反应中获得了低水平的不对称诱导作用。
• Titanium(IV)(salen) and Vanadium(V)(salen) Complexes Derived from<i>C</i>₂- and<i>C</i>₁-Symmetric Diamines for Asymmetric Cyanohydrin Synthesis
  作者：Michael North、Yuri Belokon’、Jamie Hunt

  DOI：10.1055/s-2008-1077900

  日期：2008.8

  Titanium and vanadium salen complexes have been prepared from C 2 - and Ci-symmetric acyclic diamines. All of the complexes catalysed the asymmetric addition of trimethylsilyl cyanide to benzaldehyde and the sense of asymmetric induction was determined by the nature of the substituents. The vanadium complex of a valine-derived diamine gave good results with a range of aromatic and aliphatic aldehydes

  钛和钒的salen配合物已经由C 2 -和Ci-对称的无环二胺制备。所有的配合物都催化了三甲基甲硅烷基氰化物与苯甲醛的不对称加成，并且不对称诱导的意义由取代基的性质决定。缬氨酸衍生的二胺的钒配合物与一系列芳香族和脂肪族醛产生良好的结果。