(R)-2-(benzoyloxy)non-3-enenitrile

• 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: (R)-2-(benzoyloxy)non-3-enenitrile
• 英文别名: [(E,1R)-1-cyanooct-2-enyl] benzoate
• 化学式: C₁₆H₁₉NO₂
• 分子量: 257.332
• InChiKey: HFINIZDFKHVKEY-SAAWKEMMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  19
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 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：

  苯甲酰腈 、 反-2-辛烯醛 在 titanium(IV) isopropylate 、 (S)-3,3'-bis(diethylaminomethyl)-1,1'-binaphthol 作用下， 以 四氢呋喃 为溶剂， 反应 6.0h， 生成 (S)-2-(benzoyloxy)non-3-enenitrile 、 (R)-2-(benzoyloxy)non-3-enenitrile
  参考文献：
  名称：

  BINOLAM-Ti（IV）配合物催化醛与苯甲酰基氰化物反应不对称合成O-苯甲酰基氰醇

  摘要：

  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。

  DOI：

  10.1016/j.tetasy.2005.05.031

文献信息

• 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。
• 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.