(1R)-(Methylenecyclopropyl)acetonitrile | 139242-86-7

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: (1R)-(Methylenecyclopropyl)acetonitrile
• 英文别名: (1R)-methylenecyclopropaneacetonitrile；2-[(1R)-2-methylidenecyclopropyl]acetonitrile
• CAS: 139242-86-7
• 化学式: C₆H₇N
• 分子量: 93.1283
• InChiKey: WXYNOBHDRODNBH-LURJTMIESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  7
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  23.8
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (1R)-(Methylenecyclopropyl)acetonitrile 在 chromium(VI) oxide 、 硫酸 、 二异丁基氢化铝 作用下， 生成 (1R)-亚甲基环丙烷乙酸
  参考文献：
  名称：

  Lai, Ming-Tain; Liu, Hung-Wen, Journal of the American Chemical Society, 1990, vol. 112, # 10, p. 4034 - 4035

  摘要：

  DOI：
• 作为产物：
  描述：

  2-溴-2-甲基环丙烷-1-羧酸乙酯 在 lithium aluminium tetrahydride 、 硫酸 、 sodium hydride 、 potassium carbonate 、 甲基磺酰氯 、 三乙胺 、 氯甲酸异丁酯 作用下， 以 乙醚 为溶剂， 生成 (1R)-(Methylenecyclopropyl)acetonitrile
  参考文献：
  名称：

  Lai, Ming-Tain; Liu, Hung-Wen, Journal of the American Chemical Society, 1990, vol. 112, # 10, p. 4034 - 4035

  摘要：

  DOI：

文献信息

• Lai, Ming-Tain; Liu, Hung-Wen, Journal of the American Chemical Society, 1990, vol. 112, # 10, p. 4034 - 4035
  作者：Lai, Ming-Tain、Liu, Hung-Wen

  DOI：——

  日期：——
• Synthesis of enantiomerically pure [(methylenecyclopropyl)acetyl]-CoA: the causative agent of Jamaican vomiting sickness
  作者：Ming Tain Lai、Eugene Oh、Younan Shih、Hung Wen Liu

  DOI：10.1021/jo00034a050

  日期：1992.4
• Mechanistic study on the inactivation of general acyl-CoA dehydrogenase by a metabolite of hypoglycin A
  作者：Ming Tain Lai、Li Da Liu、Hung Wen Liu

  DOI：10.1021/ja00019a040

  日期：1991.9

  General acyl-CoA dehydrogenase (GAD) is a flavin-dependent (FAD) enzyme that catalyzes the oxidation of a fatty acyl-CoA to the corresponding alpha,beta-enolyl-CoA. When GAD is exposed to (methylenecyclopropyl)acetyl-CoA (MCPA-CoA), a metabolite of hypoglycin A that is the causative agent of Jamaican vomiting sickness, time-dependent inhibition occurs with concomitant bleaching of the active-site FAD. The inactivation mechanism is generally believed to be initiated by C-alpha anion formation followed by ring fragmentation and the covalent modification of FAD. However, formation of a cyclopropyl radical intermediate through one-electron oxidation followed by ring opening and then radical recombination to yield a modified FAD is an appealing alternative. As described herein, studies of the inactivation of GAD by (1S)- and (1R)-MCPA-CoA bearing a stereospecific tritium label at C-alpha have provided direct evidence suggesting that C-alpha proton abstraction occurs during inactivation and the two diastereomers of MCPA-CoA bind to the same locus in the active site of GAD. Despite the fact that the inactivations mediated by (1R)- and (1S)-MCPA-CoA proceed at different rates, the observed partition ratios are almost identical. Using [alpha,alpha-H-2(2)]MCPA-CoA as inhibitors, we have found that the sluggish inactivation observed for (1S)-MCPA-CoA is not due to mechanistic rerouting, but is instead a result of the retardation of the initial deprotonation step. Thus, the equivalent partition ratios found in these studies clearly indicate that inactivation by either (1R)- or (1S)-MCPA-CoA follows the same chemical course. Such a lack of stereospecificity for the bond rupture at C-beta of MCPA-CoA in the enzyme active site suggests that the ring-opening step leading to inactivation is likely a spontaneous event. Since the rearrangement of alpha-cyclopropyl radicals to ring-opened alkyl radicals is extremely rapid, the ring cleavage induced by an alpha-cyclopropyl radical may bypass the chiral discrimination normally imposed by the enzyme. Thus, the mechanistic insights deduced from this study support our early notion that inactivation of GAD by MCPA-CoA is likely to proceed through a radical mechanism.
• One-pot synthesis of enantiomerically pure (methylenecyclopropyl)carbinol: a key intermediate to the synthesis of the causative agent of Jamaican vomiting sickness
  作者：Kentaro Okuma、Yuichiro Tanaka、Kanami Yoshihara、Akiyo Ezaki、Gen Koda、Hiroshi Ohta、Kenji Hara、Seiichi Kashimura

  DOI：10.1021/jo00074a015

  日期：1993.10

  Enantiomerically pure (R)- and (S)-(methylenecyclopropyl)carbinol was synthesized in a one-pot operation by the reaction of methylenetriphenylphosphane with (R)- and (S)-epichlorohydrin followed by the addition of paraformaldehyde (23 and 18 % yield). The yields of this compound were improved by the following two-step reaction. The reaction of methylenetriphenylphosphorane with epichlorohydrin afforded the corresponding (3,4-epoxybutyl)triphenylphosphonium iodide in 83% yield. This phosphonium salt further reacted with NaH followed by the addition of paraformaldehyde to give enantiomerically pure (methylenecyclopropyl)carbinol in 71% yield. The present method affords the short-step synthesis of (methylenecyclopropyl)carbinol compared with the known methods.