O-benzoyl-(S)-2-hydroxy-2-phenylacetonitrile

• 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-benzoyl-(S)-2-hydroxy-2-phenylacetonitrile
• 英文别名: (S)-2-(benzoyloxy)-2-phenylacetonitrile；(S)-cyano(phenyl)methyl benzoate；(S)-α-benzoyloxy-benzeneacetonitrile；[(S)-cyano(phenyl)methyl] benzoate
• 化学式: C₁₅H₁₁NO₂
• 分子量: 237.258
• InChiKey: AXAACNNFMJZAGJ-CQSZACIVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  50.1
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  (S)-2-phenyl-2-(trimethylsiloxy)acetonitrile 、 苯甲酰氯 在 scandium tris(trifluoromethanesulfonate) 作用下， 以 乙腈 为溶剂， 反应 1.0h， 以70%的产率得到O-benzoyl-(S)-2-hydroxy-2-phenylacetonitrile
  参考文献：
  名称：

  A one-pot esterification of chiral O-trimethylsilyl-cyanohydrins with retention of stereochemistry

  摘要：

  Enantionicrically enriched O-TMS cyanohydrins have been transformed directly into O-acyl-cyanohydrins using various anhydrides or acid chlorides in the presence of catalytic amounts of scandium(III) triflate. The reaction occurs with full retention of stereochemistry and allows the convenient measurement of enantiomeric excesses by chiral HPLC. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(02)01200-5

文献信息

• Lewis Acid–Lewis Base-Catalysed Enantioselective Addition of α-Ketonitriles to Aldehydes
  作者：Stina Lundgren、Erica Wingstrand、Christina Moberg

  DOI：10.1002/adsc.200600365

  日期：2007.2.5

  Additions of structurally diverse α-ketonitriles to aromatic and aliphatic prochiral aldehydes yielding highly enantioenriched acylated cyanohydrins were achieved using a combination of a titanium salen dimer and an achiral or chiral Lewis base. In most cases high yields and high enantioselectivities were observed. The ee was moderate in the initial part of the reaction but increased over time. This

  使用钛塞伦二聚体和非手性或手性路易斯碱的组合，可向芳香族和脂肪族手性醛中添加结构多样的α-乙腈，从而获得高度对映体富集的酰化氰醇。在大多数情况下，观察到高产率和高对映选择性。该EE是在反应的初始部分适度增加，但随着时间的推移。在添加路易斯碱之前，通过在-40℃下在存在或不存在醛和酮腈的情况下，将钛络合物保持在该温度下，可以避免这种情况，并获得更高的ee值。13 C标记实验支持了由叔胺在酮的羰基碳原子上的亲核攻击引发的机理。
• Inversion of the configuration of cyanohydrins by a mitsunobu esterification reaction
  作者：Erwin G.J.C. Warmerdam、Johannes Brussee、Chris G. Kruse、Arne van der Gen

  DOI：10.1016/s0040-4020(01)86287-6

  日期：1993.1

  Optically active (R)-cyanohydrins have been transformed into cyanohydrin esters of opposite configuration under Mitsunobu conditions and subsequently solvolyzed to (S)-cyanohydrins in high chemical and optical yield. The method works well for allylic and benzylic cyanohydrins. Cyanohydrins containing strongly electron donating substituents gave extensive racemization. Saturated aliphatic cyanohydrins

  在Mitsunobu条件下，将光学活性的（R）-氰醇转化为相反构型的氰醇酯，随后以高化学和光学收率将其溶剂化为（S）-氰醇。该方法适用于烯丙基和苄基氰醇。含有强电子给体取代基的氰醇化合物具有广泛的消旋作用。饱和脂族氰醇提供了保留原始构型的酯。根据Mitsunobu反应的机理讨论了这些结果。
• Asymmetric synthesis of O-benzoyl cyanohydrins by reaction of aldehydes with benzoyl cyanide catalysed by BINOLAM–Ti(IV) complexes
  作者：Alejandro Baeza、Carmen Nájera、José M. Sansano、José M. Saá

  DOI：10.1016/j.tetasy.2005.05.031

  日期：2005.7

  The asymmetric cyanobenzoylation of aldehydes has been carried out for the first time, by reaction with benzoyl cyanide in a process catalysed by either (R)- or (S)-3,3′-bis(diethylaminomethyl)-1,1′-binaphthol BINOLAM–Ti(IV) complexes at room temperature and without additives. The reaction can be described as an overall cyano-O-benzoylation of aldehydes where a Lewis acid–Brönsted base (LABB) dual

  醛的不对称氰基苯甲酰化首次通过在（R）-或（S）-3,3'-双（二乙基氨基甲基）-1,1'-联萘酚催化的过程中与苯甲酰基氰化物反应而进行BINOLAM–Ti（IV）络合物在室温下且无添加剂。该反应可描述为醛的整体氰基-O-苯甲酰化，其中路易斯酸-布朗斯台德碱（LABB）对催化剂的双重作用首先引发关键的对映选择性氢氰化，然后再进行O-苯甲酰化，提供对映体富集的O-苯甲酰氰醇。
• Method of preparing optically active cyanohydrin derivatives
  申请人：DUPHAR INTERNATIONAL RESEARCH B.V

  公开号：EP0601632A1

  公开（公告）日：1994-06-15

  The invention relates to a method of preparing an optically active cyanohydrin carboxylic acid ester from an optically active cyanohydrin of opposite configuration, wherein said starting cyanohydrin is converted with a carboxylic acid in the presence of a dialkyl azodicarboxylate and a triarylphosphine. The invention also relates to a method of preparing an optically active cyanohydrin of opposite configuration by a subsequent solvolysis of the ester obtained under conservation of the configuration.

  本发明涉及一种从构型相反的光学活性氰醇制备光学活性氰醇羧酸酯的方法，其中所述起始氰醇在偶氮二甲酸二烷基酯和三芳基膦存在下与羧酸进行转化。 本发明还涉及一种制备光学活性相反构型氰醇的方法，该方法是通过随后溶解在保持构型条件下获得的酯来制备光学活性相反构型的氰醇。
• Mechanistic studies on the enantioselective BINOLAM/titanium(IV)-catalyzed cyanobenzoylation of aldehydes: Part 1
  作者：Alejandro Baeza、Carmen Nájera、José M. Sansano、José M. Saá

  DOI：10.1016/j.tetasy.2011.07.006

  日期：2011.6

  The enantioselective titanium(IV)-catalyzed cyanobenzoylation of aldehydes using 1:1 BINOLAM/Ti(OiPr)(4) mixtures as a precatalyst gave O-aroyl cyanohydrins 4 with good enantiomeric excesses. The standard optimization set carried out on the assumption of Curtin-Hammett behavior, led to no amelioration.Extensive experimental and computational studies were carried out with the purpose of identifying the key mechanistic aspects governing enantioselectivity. HCN and isopropyl benzoate were detected in the reacting mixtures. This as well as the reaction response to the presence of an exogenous base, and the failure to react in the presence of Binol/Ti(OiPr)(4) mixtures, led us to propose, not a direct but an indirect process involving an enantioselective hydrocyanation step by O-benzoylation. Computational work carried out with mononuclear monomeric M-M and dinuclear mixed dimer D-IMD as catalysts support this mechanistic proposal.On the other hand, cyanobenzoylations carried out with 1:2 or higher 1:n (up to 1:5) BINOLAM/Ti(OiPr)(4) mixtures appear to involve a reversal of the enantioselection. This, together with the fact that the benzoylation of the ligated iPrOH is a slow reaction, has led us to conclude that these cyanobenzoylations do not fit within the standard Curtin-Hammett kinetic scheme. Instead, such BINOLAM/Ti(O/Pr)(4)-catalyzed cyanobenzoylations of aldehydes rather behave as non-Curtin-Hammett kinetic schemes. Further computational analysis is needed in order to make a clear distinction between Curtin-Hammett and non-Curtin-Hammett kinetic frameworks. (C) 2011 Elsevier Ltd. All rights reserved.