(R)-2-hydroxy-3-methyl-3-butenenitrile

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: (R)-2-hydroxy-3-methyl-3-butenenitrile
• 英文别名: 2-hydroxy-3-methyl-3-butenenitrile；(2r)-2-Hydroxy-3-methylbut-3-enenitrile
• 化学式: C₅H₇NO
• 分子量: 97.1167
• InChiKey: WKRMIWMWBWPVQH-YFKPBYRVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  7
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  44
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  乙酰氯 、 (R)-2-hydroxy-3-methyl-3-butenenitrile 在 吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 生成
  参考文献：
  名称：

  α-Pinene-type chiral Schiff bases as tridentate ligands in asymmetric addition reactions

  摘要：

  A group of tridentate Schiff bases derived from (+)-alpha-pinene were synthesized. The steric effects in the transition state, the importance of pi-pi stacking interactions as well as the electronic effects of aryl aldehydes according to Hammett constant values in the enantioselective addition of Et2Zn to aldehydes with the use of Schiff bases as chiral ligands are described. Also, a variety of aldehydes were cyanated using a catalyst prepared in situ from titanium tetraisopropoxide and chiral Schiff bases. The influence of a conjugated double-bond in the cyanation substrates on enantioselectivity was observed. The chemical structures of the chiral Schiff base-titanium alkoxide complexes are discussed based on their H-1 and C-13 NMR spectra. 3D models of the Zn-2-complex catalyst and Ti-complex catalyst containing alpha-pinane-type Schiff bases based on X-ray diffraction experiments are postulated. The models presented were consistent with the reported chirality of the addition product and observed ee. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2011.03.013
• 作为产物：
  描述：

  2-甲基丙烯醛 、 三甲基氰硅烷 在 titanium(IV) isopropylate 盐酸 、 (S)-2-(N-3-叔丁基亚水杨基)氨基-3-甲基-1-丁醇 作用下， 生成 (S)-2-hydroxy-3-methyl-3-butenenitrile 、 (R)-2-hydroxy-3-methyl-3-butenenitrile
  参考文献：
  名称：

  手性席夫碱-钛醇盐配合物催化的不对称碳碳键形成反应

  摘要：

  在由四异丙醇钛[Ti（O- i- Pr）4 ]和手性席夫碱原位制备的催化剂的帮助下，将三甲基甲硅烷基氰化物对映选择性加成到各种醛中，从而以高光学收率得到了相应的氰醇（最多到96％ee）。通过将席夫碱加入到钛醇盐介导的醛的甲硅烷基氰化中，可以显着提高速率。该催化剂体系还促进了双烯酮与醛的高度对映选择性反应，这导致形成光学活性的5-羟基-3-氧代酯。

  DOI：

  10.1016/s0040-4020(01)89374-1

文献信息

• Asymmetric carboncarbon bond forming reactions catalyzed by chiral Schiff base—titanium alkoxide complexes
  作者：Masahiko Hayashi、Tetsuya Inoue、Yasunori Miyamoto、Nobuki Oguni

  DOI：10.1016/s0040-4020(01)89374-1

  日期：1994.4

  The enantioselective addition of trimethylsilyl cyanide to a variety of aldehydes proceeded by the aid of a catalyst prepared in situ from titanium tetraisopropoxide [Ti(O-i-Pr)4] and chiral Schiff bases and gave the corresponding cyanohydrins in high optical yield (up to 96% e.e.). A remarkable rate enhancement was brought about by the addition of the Schiff base to the titanium alkoxide mediated

  在由四异丙醇钛[Ti（O- i- Pr）4 ]和手性席夫碱原位制备的催化剂的帮助下，将三甲基甲硅烷基氰化物对映选择性加成到各种醛中，从而以高光学收率得到了相应的氰醇（最多到96％ee）。通过将席夫碱加入到钛醇盐介导的醛的甲硅烷基氰化中，可以显着提高速率。该催化剂体系还促进了双烯酮与醛的高度对映选择性反应，这导致形成光学活性的5-羟基-3-氧代酯。
• A Facile Synthesis of Optically Active γ-Cyanoallylic Alcohols Using Asymmetric Hydrocyanation of α,β-Alkenyl Aldehydes Followed by Stereospecific [3.3]Sigmatropic Chirality Transfer of the Cyanohydrin Acetates
  作者：Hiroshi Abe、Hideaki Nitta、Atsunori Mori、Shohei Inoue

  DOI：10.1246/cl.1992.2443

  日期：1992.12

  Optically active γ-cyanoallylic alcohols were synthesized by using asymmetric hydrocyanation of α,β-alkenyl aldehydes catalyzed by peptide-titanium complex to give α-cyanoallylic alcohols (cyanohydrins) with high optical yields followed by palladium complex catalyzed [3.3]sigmatropic chirality transfer of the corresponding acetates.

  通过使用肽钛络合物催化α,β-烯基醛的不对称氰化反应，合成了光学活性的γ-氰基烯丙醇，得到高光学产率的α-氰基烯丙醇（氰基醇），随后通过钯络合物催化的相应乙酸酯的[3.3]σ迁移手性传递。
• Enantioselective trimethylsilylcyanation of some aldehydes catalyzed by chiral Schiff base-titanium alkoxide complexes
  作者：Masahiko Hayashi、Yasunori Miyamoto、Tetsuya Inoue、Nobuki Oguni

  DOI：10.1021/jo00058a037

  日期：1993.3

  A variety of aldehydes (aromatic, heteroaromatic, alpha,beta-unsaturated, and nonconjugate aliphatic aldehydes) has been trimethylsilylcyanated in highly enantiomeric excess (ee) with a catalyst prepared in situ from titanium tetraisopropoxide [Ti(O-i-Pr)4] and chiral Schiff bases. A remarkable rate enhancement was brought about by the addition of the Schiff base into the titanium alkoxide mediated silylcyanation of aldehydes. The chemical structure of chiral Schiff base-titanium alkoxide complexes is discussed based on their C-13 NMR spectra, field desorption (FD) mass spectra, and molecular weights.
• Masahiko Hayashi, Tetsuya Inoue, Yasunori Miyamoto, Nobuki Oguni, Tetrahedron, 50 (1994) N 15, S 4385-4398
  作者：Masahiko Hayashi, Tetsuya Inoue, Yasunori Miyamoto, Nobuki Oguni

  DOI：——

  日期：——
• α-Pinene-type chiral Schiff bases as tridentate ligands in asymmetric addition reactions
  作者：Magdalena Jaworska、Ewelina Błocka、Anna Kozakiewicz、Mirosław Wełniak

  DOI：10.1016/j.tetasy.2011.03.013

  日期：2011.3

  A group of tridentate Schiff bases derived from (+)-alpha-pinene were synthesized. The steric effects in the transition state, the importance of pi-pi stacking interactions as well as the electronic effects of aryl aldehydes according to Hammett constant values in the enantioselective addition of Et2Zn to aldehydes with the use of Schiff bases as chiral ligands are described. Also, a variety of aldehydes were cyanated using a catalyst prepared in situ from titanium tetraisopropoxide and chiral Schiff bases. The influence of a conjugated double-bond in the cyanation substrates on enantioselectivity was observed. The chemical structures of the chiral Schiff base-titanium alkoxide complexes are discussed based on their H-1 and C-13 NMR spectra. 3D models of the Zn-2-complex catalyst and Ti-complex catalyst containing alpha-pinane-type Schiff bases based on X-ray diffraction experiments are postulated. The models presented were consistent with the reported chirality of the addition product and observed ee. (C) 2011 Elsevier Ltd. All rights reserved.