[(1S,2S)-2-[4-(trifluoromethyl)phenyl]cyclopropyl]methanol | 201164-26-3

• 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: [(1S,2S)-2-[4-(trifluoromethyl)phenyl]cyclopropyl]methanol
• CAS: 201164-26-3
• 化学式: C₁₁H₁₁F₃O
• 分子量: 216.203
• InChiKey: NMCQHEXVLGPBQM-PSASIEDQSA-N

物化性质

• 沸点：
  270.0±35.0 °C(Predicted)
• 密度：
  1.275±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  [(1S,2S)-2-[4-(trifluoromethyl)phenyl]cyclopropyl]methanol 在 三乙基硼氢化锂 、 甲基磺酰氯 、 三乙胺 作用下， 生成 (1S,2S)-2-(p-trifluoromethylphenyl)cyclopropylmethane
  参考文献：
  名称：

  A Substituted Hypersensitive Radical Probe for Enzyme-Catalyzed Hydroxylations:  Synthesis of Racemic and Enantiomerically Enriched Forms and Application in a Cytochrome P450-Catalyzed Oxidation

  摘要：

  The syntheses of racemic and enantiomerically enriched trans-1-methyl-2-(4-(trifluoromethyl)phenyl)cyclopropane (3) and the possible oxidation products from enzyme-catalyzed hydroxylation of 3 at the methyl group are reported. The important intermediate in the production of 3 was the Weinreb amide of the 2-arylcyclopropanecarboxylic acid which could be prepared in diastereomerically pure form and which also served as an intermediate for production of the cyclic oxidation products of 3. Hydroxylation of 3 by the cytochrome P450 isozyme CYP2B1 gave cyclic and ring-opened products. The product ratios support an insertion mechanism for the enzyme-catalyzed hydroxylation reaction in which minor amounts of rearranged products are produced by radical fragmentation within the transition structure of the insertion and by a competing reaction involving a cationic species. Formation of cationic rearrangement products by a heterolytic fragmentation reaction of a first-formed protonated alcohol product is suggested on the basis of the apparent amounts of cationic products formed in the hydroxylation of 3. This pathway for cation production appears to re quire that the activated enzyme complex (equivalent to enzyme-substrate-H2O2) oxidizes substrate before water dissociates to give an iron-oxo species.

  DOI：

  10.1021/jo9712097
• 作为产物：
  描述：

  ethyl 2-(4-(trifluoromethyl)phenyl)cyclopropane-1-carboxylate 在 lithium aluminium tetrahydride 、 P-30 lipase 作用下， 以 四氢呋喃 为溶剂， 反应 194.0h， 生成 [(1S,2S)-2-[4-(trifluoromethyl)phenyl]cyclopropyl]methanol
  参考文献：
  名称：

  A Substituted Hypersensitive Radical Probe for Enzyme-Catalyzed Hydroxylations:  Synthesis of Racemic and Enantiomerically Enriched Forms and Application in a Cytochrome P450-Catalyzed Oxidation

  摘要：

  The syntheses of racemic and enantiomerically enriched trans-1-methyl-2-(4-(trifluoromethyl)phenyl)cyclopropane (3) and the possible oxidation products from enzyme-catalyzed hydroxylation of 3 at the methyl group are reported. The important intermediate in the production of 3 was the Weinreb amide of the 2-arylcyclopropanecarboxylic acid which could be prepared in diastereomerically pure form and which also served as an intermediate for production of the cyclic oxidation products of 3. Hydroxylation of 3 by the cytochrome P450 isozyme CYP2B1 gave cyclic and ring-opened products. The product ratios support an insertion mechanism for the enzyme-catalyzed hydroxylation reaction in which minor amounts of rearranged products are produced by radical fragmentation within the transition structure of the insertion and by a competing reaction involving a cationic species. Formation of cationic rearrangement products by a heterolytic fragmentation reaction of a first-formed protonated alcohol product is suggested on the basis of the apparent amounts of cationic products formed in the hydroxylation of 3. This pathway for cation production appears to re quire that the activated enzyme complex (equivalent to enzyme-substrate-H2O2) oxidizes substrate before water dissociates to give an iron-oxo species.

  DOI：

  10.1021/jo9712097

文献信息

• Hydroxylation by the Hydroperoxy-Iron Species in Cytochrome P450 Enzymes
  作者：R. Esala P. Chandrasena、Kostas P. Vatsis、Minor J. Coon、Paul F. Hollenberg、Martin Newcomb

  DOI：10.1021/ja038237t

  日期：2004.1.1

  1-(p-trifluoromethylphenyl)but-3-en-1-ol (3). In intramolecular KIE studies with dideuteriomethyl substrates (1-d(2)) and in intermolecular KIE studies with mixtures of undeuterated (1-d(0)) and trideuteriomethyl (1-d(3)) substrates, the apparent KIE for product 2 was consistently larger than the apparent KIE for product 3 by a factor of ca. 1.2. Large intramolecular KIEs found with 1-d(2) (k(H)/k(D) = 9-11

  用肝细胞色素 P450 酶、P450s 2B1、Delta2B4、Delta2B4、T302A、Delta23E1 和 T302E1 对反式-2-（对三氟甲基苯基）环丙基甲烷 (1) 的对映异构体进行羟基化，测定了分子内和分子间动力学同位素效应 (KIE)。得到两个甲基氧化产物，未重排的反式-2-（对三氟甲基苯基）环丙基甲醇（2）和重排的 1-（对三氟甲基苯基）丁-3-烯-1-醇（3）。在双氘甲基底物 (1-d(2)) 的分子内 KIE 研究和未氘化 (1-d(0)) 和三氘甲基 (1-d(3)) 底物混合物的分子间 KIE 研究中，产物 2 的表观 KIE始终比产品 3 的表观 KIE 大大约一个因子。1.2. 发现与 1-d(2) (k(H)/k(D) = 9-11 在 10 摄氏度） 的大型分子内 KIEs 显示不复杂的隧道效应与两种 P450 酶的变温研究。结果需要在竞争性或顺序性
• Catalytic enantioselective cyclopropanation of allylic alcohols using recyclable fluorous disulfonamide ligand
  作者：Tsuyoshi Miura、Keisuke Itoh、Yumi Yasaku、Naka Koyata、Yasuoki Murakami、Nobuyuki Imai

  DOI：10.1016/j.tetlet.2008.07.125

  日期：2008.9

  Cyclopropanation of allylic alcohols with Et(2)Zn and CH(2)I(2) in the presence of a catalytic amount of fluorous disulfonamide 3 afforded the corresponding cyclopropylmethanols in 69-96% yield with 49-83% ee. The fluorous ligand 3 was readily recovered from the reaction mixture by the fluorous solid-phase extraction (FSPE) and could be reused without a significant loss of the catalytic activity and enantioselectivity. (C) 2008 Elsevier Ltd. All rights reserved.