(E)-2-cyanocinnamate of (R)-pantolactone | 142635-87-8

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: (E)-2-cyanocinnamate of (R)-pantolactone
• 英文别名: (E)-2-cyanocinnamate (R)-pantolactone；(R)-Pantolactone (E)-2-cyanocinnamate；[(3R)-4,4-dimethyl-2-oxooxolan-3-yl] (E)-2-cyano-3-phenylprop-2-enoate
• CAS: 142635-87-8
• 化学式: C₁₆H₁₅NO₄
• 分子量: 285.299
• InChiKey: OPYOETSSORKLPC-RPHSKFLZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  76.4
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (E)-2-cyanocinnamate of (R)-pantolactone 在 palladium on activated charcoal 、 四氯化钛 氢氧化钾 、 sodium azide 、 五氯化磷 、 氢气 作用下， 以 乙醚 、 乙醇 、 二氯甲烷 、 丙酮 为溶剂， 反应 72.0h， 生成 (1R,2S)-1-Cyano-2-phenyl-cyclohexanecarbonyl azide
  参考文献：
  名称：

  Asymmetric Diels-Alder Reactions of Chiral (E)-2-Cyanocinnamates. 2. Synthesis of the Four 1-Amino-2-phenyl-1-cyclohexanecarboxylic Acids in Enantiomerically Pure Form

  摘要：

  High and complementary diastereoselectivities were obtained in the asymmetric Diels-Alder reactions of chiral (E)-2-cyanocinnamates with butadiene when (S)-ethyl lactate and (R)-pantolactone were used as chiral auxiliaries in the presence of TiCl4. The most selective reactions allowed the synthesis of the cycloadducts 2a and 3b, whose absolute configurations were assigned by an X-ray diffraction study of diastereoisomer 3b. The hydrolysis and subsequent hydrogenation of the stereoisomers gave the corresponding enantiomeric cyanocarboxylic acids. From these products the four 1-amino-2-phenyl-1-cyclohexanecarboxylic acids were synthesized in enantiomerically pure form following a protocol with stereocontrolled and stereodivergent transformations.

  DOI：

  10.1021/jo00104a038
• 作为产物：
  描述：

  (E)-α-cyanocinnamic acid 、 D-(-)-泛酰内酯 在 4-二甲氨基吡啶 、 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 为溶剂， 以92%的产率得到(E)-2-cyanocinnamate of (R)-pantolactone
  参考文献：
  名称：

  Reaction of 2,3-dimethyl-1,3-butadiene with chiral (E)-2-cyanocinnamates.

  摘要：

  The reactions of 2,3-dimethyl-1,3-butadiene with (E)-2-cyanocinnamates of (S)-ethyl lactate (1a) and (R)-pantolactone (1b), catalysed by TiCl4, afford enantiomerically pure cycloadducts which are easily converted into the enantiomers (1R, 6S) and (1S, 6R) of the methyl 1-cyano-3,4-dimethyl-6-phenyl-3-cyclohexen-1-carboxylate. The reactions with TiCl4 can be explained by the dienophile-TiCl4 chelate model proposed by Helmchen. The non-catalysed reaction of (1b) with the same diene takes place at 100-degrees-C, with a moderately high d.e. and reversal of selectivity.

  DOI：

  10.1016/s0957-4166(00)82189-8

文献信息

• Synthesis of a new type of conformationally constrained α,α-disubstituted-β-amino acids and β-lactams in enantiomerically pure form
  作者：Alberto Avenoza、Carlos Cativiela、Miguel París、Jesús M. Peregrina

  DOI：10.1016/0957-4166(95)00174-n

  日期：1995.6

  e-1-carboxylic acids, 9a and 9b, were obtained starting from 1,3-butadiene using Diels-Alder cycloadditions with chiral (E)-2-cyanocinnamates as key steps and following a protocol of stereocontrolled reactions. Subsequent cyclization of these conformationally constrained β-amino acids led to the corresponding α,α-disubstituted-β-lactams 10a, 10b, 11a and 11b in enantiomerically pure forms.

  光学活性的顺式- ， -图8a和8b中，和反式-1-氨基甲基-2-苯基环己烷-1-羧酸，图9a和9b中，制得使用第尔斯-阿尔德环加成与手性（E）由1,3-丁二烯开始-2 -氰基肉桂酸酯是关键步骤，并遵循立体控制反应的规程。这些构象受限的β-氨基酸的随后环化产生对映体纯形式的相应的α，α-二取代-β-内酰胺10a，10b，11a和11b。
• Asymmetric Diels-Alder reactions of chiral (E)-2-cyanocinnamates with cyclopentadiene
  作者：Carlos Cativiela、Jose A. Mayoral、Alberto Avenoza、Jesus M. Peregrina、Fernando J. Lahoz、Sergio Gimeno

  DOI：10.1021/jo00043a025

  日期：1992.8

  Several chiral derivatives of (E)-2-cyanocinnamic acid are used as trisubstituted dienophiles, and their asymmetric Diels-Alder reactions with cyclopentadiene are studied. The reactions of (E)-2-cyanocinnamates of (S)-ethyl lactate and (R)-pantolactone with cyclopentadiene, catalyzed by TiCl4, allow the synthesis of enantiomerically pure cycloadducts whose absolute configurations are assigned by an X-ray diffraction study of enantiomerically pure (1S,2S,3R,4R,5R,6R)-iodolactone. The results obtained show that the alpha-cyano group influences asymmetric induction, probably through an influence on the s-cis/s-trans equilibrium of the enoate moiety of the chiral dienophile.
• Cativiela Carlos, Avenoza Alberto, Paris Miguel, Peregrina Jesus M., J. Org. Chem, 59 (1994) N 25, S 7774-7778
  作者：Cativiela Carlos, Avenoza Alberto, Paris Miguel, Peregrina Jesus M.

  DOI：——

  日期：——
• Reaction of 2,3-dimethyl-1,3-butadiene with chiral (E)-2-cyanocinnamates.
  作者：A. Avenoza、C. Cativiela、J.A. Mayoral、J.M. Peregrina

  DOI：10.1016/s0957-4166(00)82189-8

  日期：1992.7

  The reactions of 2,3-dimethyl-1,3-butadiene with (E)-2-cyanocinnamates of (S)-ethyl lactate (1a) and (R)-pantolactone (1b), catalysed by TiCl4, afford enantiomerically pure cycloadducts which are easily converted into the enantiomers (1R, 6S) and (1S, 6R) of the methyl 1-cyano-3,4-dimethyl-6-phenyl-3-cyclohexen-1-carboxylate. The reactions with TiCl4 can be explained by the dienophile-TiCl4 chelate model proposed by Helmchen. The non-catalysed reaction of (1b) with the same diene takes place at 100-degrees-C, with a moderately high d.e. and reversal of selectivity.
• Asymmetric Diels-Alder Reactions of Chiral (E)-2-Cyanocinnamates. 2. Synthesis of the Four 1-Amino-2-phenyl-1-cyclohexanecarboxylic Acids in Enantiomerically Pure Form
  作者：Carlos Cativiela、Alberto Avenoza、Miguel Paris、Jesus M. Peregrina

  DOI：10.1021/jo00104a038

  日期：1994.12

  High and complementary diastereoselectivities were obtained in the asymmetric Diels-Alder reactions of chiral (E)-2-cyanocinnamates with butadiene when (S)-ethyl lactate and (R)-pantolactone were used as chiral auxiliaries in the presence of TiCl4. The most selective reactions allowed the synthesis of the cycloadducts 2a and 3b, whose absolute configurations were assigned by an X-ray diffraction study of diastereoisomer 3b. The hydrolysis and subsequent hydrogenation of the stereoisomers gave the corresponding enantiomeric cyanocarboxylic acids. From these products the four 1-amino-2-phenyl-1-cyclohexanecarboxylic acids were synthesized in enantiomerically pure form following a protocol with stereocontrolled and stereodivergent transformations.