(R)-(-)-α-methoxy-α-trifluoromethylphenylacetyl chloride | 111688-22-3

• 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: (R)-(-)-α-methoxy-α-trifluoromethylphenylacetyl chloride
• 英文别名: α-methoxy-α-(trifluoromethyl)phenylacetyl ester；Methyl (R)-2-methoxy-2-phenyl-3,3,3-trifluoropropionate；[R,(+)]-beta,beta,beta-Trifluoro-alpha-methoxyhydratropic acid methyl ester；methyl (2R)-3,3,3-trifluoro-2-methoxy-2-phenylpropanoate
• CAS: 111688-22-3
• 化学式: C₁₁H₁₁F₃O₃
• 分子量: 248.202
• InChiKey: RGACWXDYKJJHSQ-SNVBAGLBSA-N

物化性质

• 沸点：
  288.9±40.0 °C(Predicted)
• 密度：
  1.248±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (R)-(-)-α-methoxy-α-trifluoromethylphenylacetyl chloride 在 硫酸 作用下， 生成 (R)-(+)-α-甲氧基-α-(三氟甲基)苯乙酸
  参考文献：
  名称：

  Optical rotatory dispersion studies. CXVII. Absolute configurational assignments of some .alpha.-substituted phenylacetic acids by circular dichroism measurements

  摘要：

  DOI：

  10.1021/ja00707a024
• 作为产物：
  描述：

  (R)-3,3,3-trifluoro-2-hydroxy-2-phenylpropanoic acid 在 silver(l) oxide 作用下， 生成 (R)-(-)-α-methoxy-α-trifluoromethylphenylacetyl chloride
  参考文献：
  名称：

  Optical rotatory dispersion studies. CXVII. Absolute configurational assignments of some .alpha.-substituted phenylacetic acids by circular dichroism measurements

  摘要：

  DOI：

  10.1021/ja00707a024
• 作为试剂：
  描述：

  在 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 sodium carbonate 、 N,N'-二环己基碳二亚胺 、 (R)-(-)-α-methoxy-α-trifluoromethylphenylacetyl chloride 、 calcium chloride 作用下， 以 四氢呋喃 、 甲烷磺酸 、 乙醇 、 二氯甲烷 、 水 为溶剂， 反应 151.0h， 生成 (1S,2R,4S)-N-(tert-butoxycarbonyl)-2-hydroxy-1-hydroxymethyl-7-azabicyclo[2.2.1]heptane
  参考文献：
  名称：

  Robust trans-Amide Helical Structure of Oligomers of Bicyclic Mimics of β-Proline: Impact of Positional Switching of Bridgehead Substituent on Amide cis–trans Equilibrium

  摘要：

  Because homooligomers of 7-azabicyclo [2.2.1]-heptane-2-endo-carboxylic acid, a bridged beta-proline analogue with a substituent installed at the remote C4-bridgehead position, completely biased the amide cis-trans equilibrium to the cis-amide structure, we expected that introduction of a substituent at the C1-bridgehead position adjacent to the carboxylic acid moiety, rather than the remote C4-bridgehead position, would tip the cis trans amide equilibrium toward trans-amide structure without the aid of hydrogen bonding. Thus, in this work we established an efficient synthetic route to an optically active bicyclic analogue of 1,1-disubstituted beta-proline, bearing a substituent at the C1-bridgehead position. Crystallographic, spectroscopic, and computational studies showed that indeed oligomers of this analogue take a consistent helical structure involving all-trans-amide linkages, independently of the number of residues, from the dimer up to the octamer. Oligomers composed of (R)-beta-amino acid units form an extended left-handed helix with about 2.7 residues per turn and an approximately 4.0 angstrom rise per residue, characterized by complete lack of main-chain hydrogen bonding. This unique helical structure shows some similarity in shape to the trans-amide-based polyproline II (PPII) helix. The present helix was stable in various kinds of solvents such as alcohols. The present work provided a fundamental structural basis for future applications.

  DOI：

  10.1021/jo500916j

文献信息

• Chemoselective CaO-Mediated Acylation of Alcohols and Amines in 2-Methyltetrahydrofuran
  作者：Vittorio Pace、Pilar Hoyos、Andrés R. Alcántara、Wolfgang Holzer

  DOI：10.1002/cssc.201200922

  日期：2013.5

  Calcium oxide is proposed as an innocuous acid scavenger for the chemoselective synthesis of amide‐ and ester‐type compounds. Although these molecules have wide spread applications in organic and pharmaceutical chemistry, and a large number of routes have been designed for their synthesis, the development of more efficient and environmentally friendly acylation strategies remains an ongoing challenge

  氧化钙被提议作为酰胺和酯类化合物化学选择性合成的无害酸清除剂。尽管这些分子在有机和药物化学中具有广泛的应用，并且已经设计了许多合成途径，但是开发更有效和对环境友好的酰化策略仍然是一项持续的挑战。CaO的使用允许在酚或叔醇存在下伯醇的化学计量酰化；胺还可以在羟基存在下进行酰化反应。如果起始原料是光学纯的醇或使用手性酰化剂，则通过酰化获得手性。此外，使用更环保的溶剂2-甲基四氢呋喃（2-MeTHF），导致产量最大化。该协议已成功应用于有趣的综合N-芳基恶唑烷-2-酮中间体，用于制备利奈唑胺类化合物。
• Fluorine in fragrances: exploring the difluoromethylene (CF₂) group as a conformational constraint in macrocyclic musk lactones
  作者：Michael J. Corr、Rodrigo A. Cormanich、Cortney N. von Hahmann、Michael Bühl、David B. Cordes、Alexandra M. Z. Slawin、David O'Hagan

  DOI：10.1039/c5ob02023a

  日期：——

  The synthesis of a series of selectively fluorinated musk lactones is reported with CF₂ groups at various locations to bias conformation the ring.

  报道了一系列有选择性氟化的麝香内酯的合成，其中在不同位置有CF₂基团以偏向构象环。
• Molecular mechanics calculations and comparison of proton, fluorine, and carbon NMR diastereomer discrimination via nonbonding interactions between fluorine-labeled enantiomeric amides and enantiomerically pure chiral solvating agents
  作者：Branko S. Jursic、Zoran Zdravkovski

  DOI：10.1021/jo00071a039

  日期：1993.9

  Diastereomer discrimination of fluorine-labeled enantiomers in chloroform solutions was studied with and without two chiral solvating agents (IS and 2S) using H-1, C-13, and F-19 NMR spectroscopy. Although by C-13 NMR spectroscopy the diastereomer discrimination is not observable, changes of chemical shifts for some carbon atoms unambiguously show formation of nonbonding interactions between the enantiomers and the chiral solvating agents. The position and the ratio of signal sets in both hydrogen and fluorine NMR spectra correspond to the enantiomeric composition in the solution. On the basis of changes in the chemical shifts of enantiomers in chloroform solutions of chiral solvating agent, binding constants and binding energy differences were calculated. Using the MM2 force field, calculations were performed on binding complexes between the chiral solvating agent 2S and enantiomers 6. It was shown that demand for energy differences between diastereomeric nonbonding complexes of racemic amides and the chiral solvating amides necessary to obtain their NMR diastereomer discrimination is low for H-1, intermediary for F-19, and high for C-13 NMR.
• Optical rotatory dispersion studies. CXVII. Absolute configurational assignments of some .alpha.-substituted phenylacetic acids by circular dichroism measurements
  作者：Guenter Barth、Wolfgang Voelter、Harry S. Mosher、Edward Bunnenberg、Carl Djerassi

  DOI：10.1021/ja00707a024

  日期：1970.2