O-acetyl (S)-mandelonitrile | 119718-88-6

• 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: O-acetyl (S)-mandelonitrile
• 英文别名: (S)-cyano(phenyl)methyl acetate；cyano(phenyl)methyl acetate；(S)-O-acetylmandelonitrile；(S)-(+)-1-cyano-1-phenylmethyl acetate；(S)-2-acetoxy-phenylacetonitrile；O-acetyl-(S)-2-hydroxy-2-phenylacetonitrile；(S)-(-)-2-acetoxy-2-phenylacetonitrile；(S)-mandelonitrile acetate；[(S)-cyano(phenyl)methyl] acetate
• CAS: 119718-88-6
• 化学式: C₁₀H₉NO₂
• 分子量: 175.187
• InChiKey: MUXDFYRMYMEGCM-SNVBAGLBSA-N

物化性质

• 沸点：
  274.0±20.0 °C(Predicted)
• 密度：
  1.145±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  50.1
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  O-acetyl (S)-mandelonitrile 在 phosphate buffer 作用下， 生成 L-扁桃酸甲酯
  参考文献：
  名称：

  Kakeya, Hideaki; Sakai, Naoko; Sugai, Takeshi, Agricultural and Biological Chemistry, 1991, vol. 55, # 7, p. 1877 - 1881

  摘要：

  DOI：
• 作为产物：
  描述：

  (R)-(+)-苯乙醇腈 在 2,4,6-三甲基吡啶 作用下， 以 正己烷 、 二氯甲烷 、 溶剂黄146 为溶剂， 反应 40.5h， 生成 O-acetyl (S)-mandelonitrile
  参考文献：
  名称：

  Effenberger, Franz; Stelzer, Uwe, Chemische Berichte, 1993, vol. 126, # 3, p. 779 - 786

  摘要：

  DOI：

文献信息

• Probing the enantioselectivity of a diverse group of purified cobalt-centred nitrile hydratases
  作者：S. van Pelt、M. Zhang、L. G. Otten、J. Holt、D. Y. Sorokin、F. van Rantwijk、G. W. Black、J. J. Perry、R. A. Sheldon

  DOI：10.1039/c0ob01067g

  日期：——

  In this study a diverse range of purified cobalt containing nitrile hydratases (NHases, EC 4.2.1.84) from Rhodopseudomonas palustris HaA2 (HaA2), Rhodopseudomonas palustris CGA009 (009), Sinorhizobium meliloti 1021 (1021), and Nitriliruptor alkaliphilus (iso2), were screened for the first time for their enantioselectivity towards a broad range of chiral nitriles. Enantiomeric ratios of >100 were found for the NHases from HaA2 and CGA009 on 2-phenylpropionitrile. In contrast, the Fe-containing NHase from the well-characterized Rhodococcus erythropolis AJ270 (AJ270) was practically aselective with a range of different α-phenylacetonitriles. In general, at least one bulky group in close proximity to the α-position of the chiral nitriles seemed to be necessary for enantioselectivity with all NHases tested. Nitrile groups attached to a quaternary carbon atom were only reluctantly accepted and showed no selectivity. Enantiomeric ratios of 80 and >100 for AJ270 and iso2, respectively, were found for the pharmaceutical intermediate naproxennitrile, and 3-(1-cyanoethyl)benzoic acid was hydrated to the corresponding amide by iso2 with an enantiomeric ratio of >100.

  在本研究中，首次对来自红假单胞菌HaA2（HaA2）、红假单胞菌CGA009（009）、豌豆根瘤菌1021（1021）和嗜碱氮裂解菌（iso2）的多种纯化钴含氮裂解酶（NHases，EC 4.2.1.84）对一系列手性腈的立体选择性进行了筛选。对于2-苯基丙腈，来自HaA2和CGA009的NHases的立体异构比大于100。相比之下，来自已知红球菌AJ270（AJ270）的含铁NHase对一系列不同α-苯基乙腈实际上没有选择性。总的来说，对于所有测试的NHases来说，似乎至少需要一个在α-位附近的大体积基团才能实现立体选择性。连接在四级碳原子上的腈基团仅勉强被接受，并且没有显示出选择性。对于药物中间体萘普生腈，AJ270和iso2的立体异构比分别为80和大于100；iso2还将3-（1-氰乙基）苯甲酸水合为相应的酰胺，立体异构比大于100。
• An Efficient Titanium Catalyst for Enantioselective Cyanation of Aldehydes: Cooperative Catalysis
  作者：Zhipeng Zhang、Zheng Wang、Ruzhou Zhang、Kuiling Ding

  DOI：10.1002/anie.201002127

  日期：2010.9.10

  Two‐in‐one: The integration of two salen/TiO units into one molecule allows the enantioselective cyanation of aldehydes to afford the enantioenriched natural or nonnatural cyanohydrin derivatives with turnover numbers of 1960–172 000 and ee values up to 97 % (see scheme). Some of the cyanohydrin derivatives are key intermediates for the synthesis of chiral pharmaceuticals or agrochemicals.

  二合一：将两个salen /TiO单元整合到一个分子中可以使醛的对映体选择性氰化，从而提供对映体富集的天然或非天然氰醇衍生物，其周转数为1960–172 000，ee 值高达97％（参见方案）。一些氰醇衍生物是合成手性药物或农用化学品的关键中间体。
• Enantioselective cyanosilylation of aldehydes catalyzed by novel camphor derived Schiff bases-titanium(IV) complexes
  作者：Ewelina Błocka、Mariusz J. Bosiak、Mirosław Wełniak、Agnieszka Ludwiczak、Andrzej Wojtczak

  DOI：10.1016/j.tetasy.2014.03.001

  日期：2014.4

  Five tridentate Schiff bases have been prepared from (1R,2S,3R,4S)-3-amino-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ol and salicylaldehydes. X-ray structure investigation revealed differences in their molecular conformation, and their titanium(IV) complexes have been studied with NMR techniques. Among them the complex with the Schiff base obtained from 2-hydroxy-3-isopropylbenzaldehyde, is the most selective

  五三齿席夫碱已经从（1制备- [R，2小号，3 - [R，4小号）-3-氨基- 1,7,7-三甲基二环[2.2.1]庚-2-醇和水杨醛。X射线结构的调查显示在它们的分子构象的差异，和它们的钛（IV）络合物进行了研究NMR技术。它们之间的复合物与由2-羟基-3-异丙基苯甲醛得到的席夫碱，为脂肪族，脂环族，芳族，杂芳族和醛的硅氰化反应最有选择性的催化剂。最高的对映选择性，> 99％时，在加入三甲基氰硅烷的给肉桂醛实现。
• Highly Enantioselective Cyanosilylation of Aldehydes Catalyzed by Novel β-Amino Alcohol−Titanium Complexes
  作者：Yan Li、Bin He、Bo Qin、Xiaoming Feng、Guolin Zhang

  DOI：10.1021/jo0488356

  日期：2004.11.1

  The β-amino alcohol 1b−Ti(Oi-Pr)4 complex has been shown to catalyze the enantioselective cyanosilylation of aldehydes efficiently. In the presence of 5 mol % of 1b−Ti(Oi-Pr)4 complex catalyst, the aromatic, conjugated, heteroaromatic, and aliphatic aldehydes were converted to their corresponding trimethylsilyl ethers of cyanohydrins in 90−99% yields with up to 94% ee under mild conditions.

  β-氨基醇1b -Ti（O i -Pr）4配合物已显示出可有效催化醛的对映选择性氰基硅烷化反应。在5摩尔％的1b -Ti（O i -Pr）4络合催化剂存在下，芳族，共轭，杂芳族和脂族醛以90-99％的产率转化为相应的氰醇三甲基甲硅烷基醚，产率最高为94 ％ee在温和条件下。
• 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