(R)-(+)-2,3,4,5,6-pentafluorostyrene oxide | 121680-77-1

• 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)-(+)-2,3,4,5,6-pentafluorostyrene oxide
• 英文别名: (R)-(+)-pentafluorostyrene oxide；(R)-1-(pentafluorophenyl)oxirane；(R)-(pentafluorophenyl)oxirane；(R)-pentafluorostyrene oxide；(pentafluorophenyl)oxirane；(R)-2-(perfluorophenyl)oxirane；(2R)-2-(2,3,4,5,6-pentafluorophenyl)oxirane
• CAS: 121680-77-1
• 化学式: C₈H₃F₅O
• mdl: MFCD00077569
• 分子量: 210.103
• InChiKey: ZUZPTXICNGFRDG-REOHCLBHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (R)-(+)-2,3,4,5,6-pentafluorostyrene oxide 在 dilithium tetrabromocuprate 、 三正丁基氢锡 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 生成 (S)-(-)-α-甲基-2,3,4,5,6-五氟苯甲醇
  参考文献：
  名称：

  α-甲基羧酸衍生物的不对称合成。环氧化物的酸性开环中的立体化学

  摘要：

  通过微生物产生的环氧化物与三甲基铝的反应制备光学活性的α-甲基羧酸衍生物。通过MO计算讨论了开环反应的立体化学。

  DOI：

  10.1016/s0040-4039(00)74487-x
• 作为产物：
  描述：

  2,3,4,5,6-五氟苯乙烯 在 chiral iron "twin coronet" porphyrin 亚碘酰苯 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 生成 (R)-(+)-2,3,4,5,6-pentafluorostyrene oxide 、 (R)-(+)-2,3,4,5,6-pentafluorostyrene oxide
  参考文献：
  名称：

  手性联四氢萘带“双冠”卟啉的合成。苯乙烯衍生物的催化和不对称环氧化

  摘要：

  在卟啉的两个面上带有光学活性 1,1'-双四氢萘衍生物的“双冠”卟啉被制备为模拟细胞色素 P-450 的对映选择性氧化催化剂。相应的铁 (III) 卟啉的失色异构体在高 ee (61–89%) 和高产物选择性下催化被吸电子基团取代的苯乙烯的环氧化。

  DOI：

  10.1246/cl.1991.1933

文献信息

• Asymmetric Epoxidation of Simple Olefins by Chiral Bitetralin-Linked "Twin-Coronet" Porphyrin Catalysts.
  作者：Yoshinori Naruta、Nobuo Ishihara、Fumito Tani、Kazuhiro Maruyama

  DOI：10.1246/bcsj.66.158

  日期：——

  Catalytic and asymmetric epoxidation of styrenes and related aryl substituted olefins with the iron complexes of chiral bitetralin (Bitet)–linked “twin–coronet” porphyrins was performed with iodosylbenzene as an oxidant. Among two topological isomers of the catalyst, the eclipsed one (5b) showed higher enantioselectivity than the staggered (6b). With 5b, the resulting epoxides, except for the olefins bearing an electron–donating substituent, were obtained in good to excellent enantioselectivity (54—96% ee), especially for the styrenes with electron–withdrawing substituent(s). Being different from other porphyrin–based chiral catalysts, the catalyst 5b is robust enough under the applied oxidation conditions to exhibit chiral epoxidation with the same ee and the same rate as those of the initial period of the reaction even after about 500 turnovers. The Bitet catalyst is superior in the epoxide enantioselectivity than the corresponding chiral binaphthalene (Binap)–linked catalyst (3b). In the reactions with the catalysts 3b and 5b, good correlation in epoxide ees was observed. Increase of the epoxide ee in the reaction with the Bitet catalyst was elucidated by the shape and size of the reaction cavities of the Bitet were tighter than those of the latter. The observed ees of the substituted styrene oxides showed good correlation with Σσ+ values of their substituent(s). In the reaction with the electron–deficient olefins, π–π* interaction between the HOMO of the electron–rich Bitet auxiliary ring and the LUMO of the electron–deficient aryl ring of the substrate are pointed out as the key for the realization of high ees. Some nitrostyrenes, however, gave rather lower ees in spite of rather higher degree of their electron deficiency. This deviation was elucidated by the mismatching of their frontier orbitals.

  使用碘代氧化苯作为氧化剂，通过手性双四氢萘（Bitet）连接的“双冠”卟啉铁配合物对苯乙烯及相关芳香取代烯烃进行催化和不对称环氧化反应。在两种拓扑异构体的催化剂中，重叠式（5b）表现出比交错式（6b）更高的手性选择性。使用5b催化剂，除了带有供电子取代基的烯烃外，所得环氧化物均在良好的手性选择性（54—96% 对映体过量）下获得，尤其是带有吸电子取代基的苯乙烯。与其他基于卟啉的手性催化剂不同，催化剂5b在应用的氧化条件下足够稳定，即使在约500次周转后，也能在相同对映体过量和相同速率下展示不对称环氧化反应，如同反应初期一样。Bitet催化剂在环氧化物的对映选择性上优于相应的双萘（Binap）连接的催化剂（3b）。在使用催化剂3b和5b的反应中，环氧化物的对映体过量呈现出良好的相关性。通过Bitet催化剂反应腔的形状和大小比后者更紧密，解释了环氧化物对映体过量的增加。取代苯乙烯氧化物的观测对映体过量与其取代基的Σσ+值显示出良好的相关性。在电子缺乏烯烃的反应中，指出富电子Bitet辅环的HOMO与电子缺乏基质的芳香环的LUMO之间的π-π*相互作用是实现高对映体过量的关键。然而，一些硝基苯乙烯尽管具有更高的电子缺乏程度，却给出了较低的对映体过量。这种偏差通过它们前沿轨道的不匹配得到了解释。
• Synthesis of optically active oxazolines from optically active epoxides
  作者：Junko Umezawa、Osamu Takahashi、Keizo Furuhashi、Hiroyuki Nohira

  DOI：10.1016/s0957-4166(00)86221-7

  日期：1994.3

  The reaction of optically active terminal epoxides, which were produced by a microbial reaction, with acetonitrile in the presence of a protic acid or Lewis acid was studied. 1,2-Epoxyoctane, 2-methyl-1,2-epoxyhexane, and pentafluorostyrene oxide gave the corresponding 4-substituted 2-methyl-2-oxazoline derivatives with moderate to excellent regioselectivity. The reactions proceeded with an inversion

  研究了在质子酸或路易斯酸存在下，由微生物反应产生的旋光性末端环氧化物与乙腈的反应。1，2-环氧辛烷，2-甲基-1，2-环氧己烷和五氟苯乙烯氧化物得到相应的4-取代的2-甲基-2-恶唑啉衍生物，具有中等至优异的区域选择性。反应在AlCl 3-或SnCl 4催化的条件下以高立体特异性的不对称中心反转进行，而在HF-或CF 3 SO 3下发生部分消旋。H催化条件。所用的酸和环氧化物上的取代基影响了恶唑啉形成的立体特异性和区域选择性。通过2-氨基辛醇将具有高立体特异性的4-己基-2-甲基-2-恶唑啉转化为2-氨基辛酸。
• Enantioselectivity in the ritter-type substitution reaction via qpisulfonium ion: Retention of configuration
  作者：Akio Toshimitsu、Chitaru Hirosawa、Shigeo Tanimot

  DOI：10.1016/s0040-4039(00)92159-2

  日期：1991.1

  Ritter-type substitution reaction of optically active β-hydroxyalkyl phenyl sulfides was found to proceed with retention fo configuration through the participation of phenylthio group to afford optically active amides.

  发现旋光性β-羟烷基苯硫醚的Ritter型取代反应通过苯硫基的参与以保留构型进行，从而提供旋光性酰胺。
• Retention of configuration in the ritter-type substitution reaction of chiral β-arylthio alcohols through the anchimeric assistance of the arylthio group
  作者：Akio Toshimitsu、Chitaru Hirosawa、Kohei Tamao

  DOI：10.1016/s0040-4020(01)85367-9

  日期：1994.1

  In chiral alcohols bearing a phenylthio group at the β carbon atom. the hydroxy group is replaced by nitriles through the anchimeric assistance of the phenylthio group to afford chiral amides with retention of configuration. This stereospecific Ritter-type reaction has been utilized in the conversion of chiral glycidol derivatives to chiral cyclic imino ethers such as oxazolines bearing an arylthio

  在β碳原子上带有苯硫基的手性醇中。通过苯硫基的手性辅助，羟基被腈取代，得到保留构型的手性酰胺。该立体有规的Ritter型反应已用于手性缩水甘油衍生物向手性环状亚氨基醚如带有芳硫基的恶唑啉的转化中。
• Synthesis of Novel Chiral Diazole Derivative Ligands for the Enantioselective Addition of Diethylzinc to Benzaldehyde
  作者：Hiyoshizo Kotsuki、Masahiro Wakao、Hiroyuki Hayakawa、Tomoyasu Shimanouchi、Motoo Shiro

  DOI：10.1021/jo961388c

  日期：1996.1.1

  The high-pressure-promoted reaction of epoxides with pyrazoles and imidazoles provided access to a variety of chiral diazole derivative ligands such as 11-23. Furthermore, chiral pyrazoles 26 and 27, which have a primary alcohol side chain, were also prepared from (+)-camphopyrazole 4. Each of these chiral diazole ligands was used for the catalytic enantioselective addition of diethylzinc to benzaldehyde

  环氧化物与吡唑和咪唑的高压促进反应提供了接触各种手性二唑衍生物配体的途径，例如11-23。此外，还由（+）-樟脑吡唑4制备了具有伯醇侧链的手性吡唑26和27。这些手性二唑配体中的每一种都用于将二乙基锌催化对映选择性加成至苯甲醛。对于16和18，获得了最佳结果：在两种情况下均达到93％ee，并且观察到反向不对称诱导。在X射线晶体学数据的基础上，提供了一种有效的不对称感应机制。