1,2-diphenyl-2-fluoro-1-hydroxyethane | 88858-93-9

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: 1,2-diphenyl-2-fluoro-1-hydroxyethane
• 英文别名: 2-fluoro-1,2-diphenylethanol
• CAS: 88858-93-9
• 化学式: C₁₄H₁₃FO
• 分子量: 216.255
• InChiKey: HWAQOGMSTLINNF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  Stilbene oxide 在 tetrabutylammonium bifluoride potassium hydrogen bifluoride 作用下， 反应 120.0h， 以72%的产率得到1,2-diphenyl-2-fluoro-1-hydroxyethane
  参考文献：
  名称：

  四氢三氟化四丁基铵：在固-液相转移催化条件下，环氧化物向立体选择性转化为氟代醇的有效催化剂。

  摘要：

  四丁基三氟化氢铵在环氧乙烷的开环反应中是一种高效且易于处理的氢氟化剂，在固液PTC条件下可获得良好或优异的氟代醇收率。

  DOI：

  10.1016/s0040-4039(00)97281-2

文献信息

• Metal-Free and User-Friendly Regioselective Hydroxyfluorination of Olefins
  作者：Daniel M. Sedgwick、Inés López、Raquel Román、Nanako Kobayashi、Otome E. Okoromoba、Bo Xu、Gerald B. Hammond、Pablo Barrio、Santos Fustero

  DOI：10.1021/acs.orglett.8b00681

  日期：2018.4.20

  inexpensive reagents has been developed. This new approach displays a broader scope than previously reported methodologies and has been applied to the late-stage fluorination of a complex molecule, giving rise to a fluorosteroid derivative. The stereochemistry of the process has also been studied in some detail.

  已经开发出一种简单、用户友好、无金属的方案，用于使用易于获得且廉价的试剂对烯烃进行区域选择性反马尔可夫尼科夫氢氟化。这种新方法比以前报道的方法显示出更广泛的范围，并已应用于复杂分子的后期氟化，从而产生氟类固醇衍生物。该过程的立体化学也已得到一些详细的研究。
• Palladium-catalyzed intermolecular fluoroesterification of styrenes: exploration and mechanistic insight
  作者：Haihui Peng、Zheliang Yuan、Hao-yang Wang、Yin-long Guo、Guosheng Liu

  DOI：10.1039/c3sc50690h

  日期：——

  A novel palladium-catalyzed intermolecular oxidative fluoroesterification of vinylarenes has been developed using NFSI, one of the mildest electrophilic fluorinating reagents. The reaction presents an efficient synthetic pathway to afford a series of α-monofluoromethylbenzyl carboxylates in good to excellent yields. Rather than following an electrophilic fluorination pathway, the reaction is initiated through oxidation of Pd(0) to a Pd(II) fluoride complex by NFSI, followed by fluoropalladation of a styrene to generate an α-monofluoromethylbenzyl–Pd intermediate. Generally, reductive elimination of benzyl–PdII complexes is favored with relatively strong oxy-nucleophiles to afford C–O bonds. This reaction, however, exhibited the opposite reactivity: strong acids with weak nucleophilicity, such as CF3CO2H and CCl3CO2H, were prone to afford the fluoroesterification product, while weak acids with strong nucleophilicity, such as HOAc and BzOH, did not deliver the C–O bond product. Further mechanistic studies determined that Csp3–Pd(O2CR), a key intermediate, was generated through ionic ligand exchange between benzyl–Pd(NZ2) and CF3CO2H, and the final C–O bond was possibly formed through reductive elimination of a high-valent Csp3–Pd(O2CR) complex via an SN2-type nucleophilic attack pathway.

  一种新型钯催化的乙烯基芳烃分子间氧化性氟酯化反应已被开发，使用的试剂是NFSI，即一种最温和的亲电氟化试剂。该反应提供了一条高效的合成途径，能够以良好至优异的产率获得一系列α-单氟甲基苄基羧酸酯。反应并非遵循亲电氟化途径，而是通过NFSI将Pd(0)氧化为Pd(II)氟化物配合物，随后进行氟钯化作用于苯乙烯生成α-单氟甲基苄基-Pd中间体。通常情况下，与相对较强的氧亲核试剂反应有利于实现苄基-PdII配合物的还原消除，从而形成C-O键。然而，在此反应中表现出了相反的反应性：易与强酸（弱亲核性）如CF3CO2H和CCI3CO2H形成氟酯化产物，而与强亲核性弱酸如HOAc和BzOH则无法形成C-O键产物。进一步的机理研究表明，关键中间体Csp3-Pd(O2CR)是通过苄基-Pd(NZ2)与CF3CO2H之间的离子配体交换生成的，最终的C-O键很可能是通过高氧化态Csp3-Pd(O2CR)配合物的还原消除形成的，该过程可能涉及SN2型亲核攻击路径。
• Potassium dihydrogen trifluoride: a novel fluorinating reagent for ring-opening of epoxides
  作者：Masanori Tamura、Motonari Shibakami、Takashi Arimura、Shigeru Kurosawa、Akira Sekiya

  DOI：10.1016/0022-1139(94)03175-y

  日期：1995.1

  It has been found that potassium dihydrogen trifluoride is an efficient and easy-to-handle solid reagent for the ring-opening reaction of epoxides giving fluorohydrins regio- and stereo-selectively. The reaction proceeds via cis-addition of HF to the epoxide.

  已经发现，三氟化二氢钾是一种有效且易于处理的固体试剂，用于环氧化物和立体选择性地产生氟代醇的环氧化物的开环反应。该反应通过将HF顺式加成到环氧化物上而进行。
• (Salen)chromium Complex Mediated Asymmetric Ring Opening of meso- and Racemic Epoxides with Different Fluoride Sources
  作者：Günter Haufe、Stefan Bruns

  DOI：10.1002/1615-4169(200202)344:2<165::aid-adsc165>3.0.co;2-1

  日期：2002.2

  as cyclopentene oxide and cycloheptene oxide the corresponding fluorohydrins were isolated in 80% and 82% yield with 65% and 62% ee, respectively. In case of ring opening under similar conditions of the racemic styrene oxide or phenyl glycidyl ether 83% and 75% of the fluorohydrins with fluorine in the primary position were isolated with 74% ee and 65% ee, respectively. Tetrahydronaphthalene oxide yielded

  在化学计量或化学计量稍低的雅各布森对映纯（salen）氯化铬络合物A存在下，用不同的氟化试剂对五个内消旋和三个外消旋环氧化物进行不对称开环，得到了相应的旋光性邻位氟代醇。氟化银被用作氟化物来源之一无论是在卜存在4 Ñ + ħ 2 ˚F 3 -在乙醚或乙腈。从氧化环己烯（起始后者反应1）显示出在所形成的最大fluorohydrin 72％ee的2以90％的产率分离。从其他介观-环氧化合物，例如环戊烯氧化物和环庚烯氧化物，分离相应的氟代醇，产率分别为80％和82％，ee分别为65％和62％。在外消旋的苯乙烯氧化物或苯基缩水甘油醚的类似条件下开环的情况下，分别以74％ee和65％ee分离出83％和75％的氟醇，其中氟位于主要位置。四氢萘氧化物产生反式-（23％ee）和顺式-2-氟-3,4-苯并环己烯醇（2％ee）的2：1混合物，表明存在竞争的S N 2和S N 1型开环。其他环氧化物，例如环辛烯
• Site-selective fluorination of organic compounds using 1-alkyl-4-fluoro-1,4-diazabicyclo[2.2.2]octane salts (selectfluor reagents)
  作者：G. Sankar Lal

  DOI：10.1021/jo00062a023

  日期：1993.5

  The new ''N-F''-type electrophilic reagent family of 1-alkyl-4-fluoro-1,4-diazabicyclo[2.2.2]octane salts8d (derived from elemental fluorine (F2) and 1-alkyl-1,4-diazabicyclo[2.2.2]octane salts) has been found to be very effective for the fluorination of a wide variety of organic substrates. These include steroidal enol acetates and silyl enol ethers, phenyl-substituted olefins, sulfides bearing alpha-H atoms, certain carbanions, and mildly activated aromatic compounds. The products were obtained with good yields and regioselectivity under very mild reaction conditions.