(2S)-2-(3-硝基苯基)环氧乙烷 | 138809-93-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: (2S)-2-(3-硝基苯基)环氧乙烷
• 中文别名: (S)-3-硝基苯基环氧乙烷
• 英文名称: (S)-(+)-(3-nitrophenyl)oxirane
• 英文别名: (S)-3-nitrostyrene oxide；(2S)-2-(3-nitrophenyl)oxirane
• CAS: 138809-93-5
• 化学式: C₈H₇NO₃
• 分子量: 165.148
• InChiKey: VVZFDVJTIOLMKC-MRVPVSSYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  12
• 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：
  58.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2S)-2-(3-硝基苯基)环氧乙烷 在 epoxide hydrolase from Vigna radiata; variant VrEH_2M263Q 作用下， 以 aq. phosphate buffer 、 二甲基亚砜 为溶剂， 生成 (R)-(-)-1-(3-nitrophenyl)-1,2-ethanediol
  参考文献：
  名称：

  重编程环氧水解酶，以提高苯乙烯氧化物支架水解中的对映体收敛性

  摘要：

  通过环氧水解酶的对映体收敛水解是一种重要的邻位二醇合成的有前途的方法。但是，天然酶的区域选择性差会导致苯乙烯氧化物的酶促水解中对映体收敛性低。在此，根据结构信息重新设计了263号残基，并使用“优化的氨基酸字母”通过定点修饰构建了一个智能变体文库，以提高来自Vigna radiata（Vr EH2）的环氧水解酶的区域选择性。M263Q变体对间位异构体R异构体的区域选择性系数（r）与野生型相比，预取代的苯乙烯氧化物提高了40-63倍，变体M263V对对位取代的苯乙烯氧化物的R异构体也表现出更高的区域选择性，从而提高了苯乙烯氧化物支架水解中的对映体收敛性。结构上的洞察力表明263号残基在通过改变结合环境来调节底物结合构象中的关键作用。此外，亲核残基Asp101和环氧化物的两个碳原子之间的攻击距离差异增加，为区域选择性的提高提供了证据。几种易于合成的高价值邻位二醇（> 88％收率，90％–98％ 

  DOI：

  10.1002/adsc.202000898
• 作为产物：
  描述：

  2-溴-3'-硝基苯乙酮 在 sodium hydroxide 、 sodium tetrahydroborate 、 2-(3-NO₂-Ph)-1,3,2-dioxaborolane-(4R,5R)-dicarboxylic acid 作用下， 以 四氢呋喃 为溶剂， 生成 (2S)-2-(3-硝基苯基)环氧乙烷
  参考文献：
  名称：

  Chiral styrene oxides from α-haloacetophenones using NaBH4 and TarB-NO2, a chiral Lewis acid

  摘要：

  High enantio selectivities are obtained for the preparation of chiral styrene oxides through reduction of a-haloacetophenones using TarB-NO2 reagent and the inexpensive and mild reducing agent NaBH4. The epoxides are easily obtained in up to 95% ee through routine acid-base workup of the product alcohols. Either the (R) or (S) epoxide can be obtained by using the appropriate L- or D-tartaric acid starting material in the TarB-NO, reagent. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2005.11.011

文献信息

• Synthesis of Chiral Bitetralin-strapped “Twin Coronet” Porphyrins. Catalytic and Asymmetric Epoxidation of Styrene Derivatives
  作者：Yoshinori Naruta、Nobuo Ishihara、Fumito Tani、Kazuhiro Maruyama

  DOI：10.1246/cl.1991.1933

  日期：1991.11

  “Twin-coronet” porphyrins bearing optically active 1,1′-bitetrahydronaphthalene derivatives on the both faces of the porphyrin were prepared as enantioselective oxidation catalysts modeling on cytochrome P-450s. The eclipsed isomer of the corresponding iron(III) porphyrins catalyzed epoxidation of styrenes substituted with electron-withdrawing groups in high e.e. (61–89%) and high product selectivity

  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。
• Highly Selective Hydrolytic Kinetic Resolution of Terminal Epoxides Catalyzed by Chiral (salen)Co^III Complexes. Practical Synthesis of Enantioenriched Terminal Epoxides and 1,2-Diols
  作者：Scott E. Schaus、Bridget D. Brandes、Jay F. Larrow、Makoto Tokunaga、Karl B. Hansen、Alexandra E. Gould、Michael E. Furrow、Eric N. Jacobsen

  DOI：10.1021/ja016737l

  日期：2002.2.1

  The hydrolytic kinetic resolution (HKR) of terminal epoxides catalyzed by chiral (salen)Co(III) complex 1 x OAc affords both recovered unreacted epoxide and 1,2-diol product in highly enantioenriched form. As such, the HKR provides general access to useful, highly enantioenriched chiral building blocks that are otherwise difficult to access, from inexpensive racemic materials. The reaction has several

  由手性 (salen)Co(III) 配合物 1 x OAc 催化的末端环氧化物的水解动力学拆分 (HKR) 提供了回收的未反应环氧化物和高度对映体富集形式的 1,2-二醇产物。因此，HKR 提供了从廉价的外消旋材料中获得有用的、高度对映体富集的手性结构单元的通用途径，而这些结构单元在其他方面难以获得。从实用的角度来看，该反应具有几个吸引人的特点，包括使用 H(2)O 作为反应物和低负载 (0.2-2.0 mol%) 的可回收、市售催化剂。此外，HKR 显示出非凡的范围，因为可以将各种空间和电子变化的环氧化物分解为 > 或 = 99% ee。相应的 1,2-二醇是使用 0.45 当量的 H(2)O 在良好到高对映体过量中产生的。提供了用于分离高度对映体富集的环氧化物和二醇以及催化剂回收和再循环的有用和通用的协议。HKR 反应的选择性因子 (k(rel)) 通过测量约 ee 的产物 ee 来确定。20%
• 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。
• Stereo- and Enantioselective Alkene Epoxidations: A Comparative Study of D4- and D2-Symmetric Homochiral trans-Dioxoruthenium(VI) Porphyrins
  作者：Rui Zhang、Wing-Yiu Yu、Hong-Zhe Sun、Wei-Sheng Liu、Chi-Ming Che

  DOI：10.1002/1521-3765(20020603)8:11<2495::aid-chem2495>3.0.co;2-g

  日期：2002.6.3

  dioxoruthenium(VI) porphyrins proceeds through the rate-limiting formation of a benzylic radical intermediate; the observed enantioselectivity (eeobs) depends on both the facial selectivity of the first C-O bond formation step and the diastereoselectivity of the subsequent epoxide ring closure. To account for the observed facial selection, "side-on" and "top-on" approach transition state models are examined

  D4-和D2-对称的同手性反式二氧杂钌（VI）卟啉，[RuVI（D4-Por *）O2]（1）和[RuVI（D2-Por *）O2]（2a）的化学计量对映选择性烯烃环氧化的机理），在存在吡唑（Hpz）的条件下，通过UV / Vis分光光度法对有机产物进行了分析。苯乙烯氧化的对映选择性比取代基电子效应更容易受到空间效应的影响。通过使用1作为氧化剂，对3-取代的和顺式-二取代的苯乙烯进行环氧化，可实现高达72％的ee，而在与2-取代和反-二取代的苯乙烯的反应中，对映选择性仅为20-40％。络合物2a在高达88％ee的条件下将2-取代的苯乙烯氧化为环氧化物。它与反式烯烃的反应对映选择性更高（67％ee），而与顺式烯烃的反应（40％ee）更高。根据二维NOESY NMR研究，发现2a在苯中的构型比在二氯甲烷中的构型更开放，这解释了观察到的其与烯烃反应的溶剂依赖性对映选择性。手性二氧杂钌（VI）卟啉
• Mechanistic Investigation of the Oxidation of Aromatic Alkenes by Monooxoruthenium(IV). Asymmetric Alkene Epoxidation by Chiral Monooxoruthenium(IV) Complexes
  作者：Wai-Hong Fung、Wing-Yiu Yu、Chi-Ming Che

  DOI：10.1021/jo980755c

  日期：1998.10.1

  'The oxoruthenium(IV) complexes [Ru-IV(terpy)(6,6'-Cl-2-bpy)O](ClO4)(2) (1a; terpy = 2,2':6',2 "-terpyridine; 6,6'-Cl-2-bpy = 6,6'-dichloro-2,2'-bipyridine), [Ru-IV(terpy)(tmeda)O](ClO4)(2) (1b; tmeda = N,N,N',N'-tetramethylethylenediamine), [Ru-IV(Cn)(bpy)O](ClO4)(2) (1c; Cn = 1,4,7-trimethyl-1,4,7-triazacyclononane), and [Ru-IV(PPz*)(bpy)O](ClO4)(2) (1d; PPz* = 2,6-bis[(4S,7R)-7,8,8-trimethyl-4,5,6,7-tetrahydro-4,7-methanoindazol-2-yl]pyridine) are effective for the epoxidation of aromatic alkenes in acetonitrile at ambient conditions. Their reactions with cis-alkenes such as cis-beta-methylstyrene and cis-beta-deuteriostyrene afford epoxides nonstereospecifically. The observation of the inverse secondary kinetic isotope effect for the beta-d(2)-styrene oxidations [k(H)/k(D) = 0.87 (1b), 0.86 (1d)], but not for alpha-deuteriostyrene (k(H)/k(D) = 0.98 for 1b and 1d), indicates that C-O bond formation is more advanced at the beta-carbon atom than at the alpha carbon, i.e., a stepwise mechanism. The second-order rate constants (k(2)) for the styrene oxidations are weakly dependent on the E degrees(Ru-IV/III) values of the oxoruthenium(IV) complexes, and both electron-withdrawing and -donating para substituents mildly accelerate the oxidation reaction of styrene. These findings discount strongly the intermediaries of an alkene-derived cation radical and a carbocation. A linear free-energy relationship between the second-order rate constants for the para-substituted styrene oxidations and the total substituent effect (TE) parameters has been established: rho(TE .) = +0.43 (R = 0.99) for 1b, +0.50 (R = 0.98) for 1c, and +0.37 (R = 0.99) for 1d (Wu, Y.-D.; Wong, C.-L.; Chan, K. W.; Ji, G.-Z.; Jiang, X.-K. J. Org. Chem. 1996, 61, 746). This suggests that the oxidation of aromatic alkenes by oxoruthenium(IV) complexes should proceed via the rate-limiting formation of a benzylic radical intermediate. Oxidation of styrene and cis- and trans-beta-methylstyrenes by the chiral oxoruthenium-(IV) complex Id attains moderate enantioselectivities, in which the production of cis-epoxide is more enantioselective than the trans counterpart. The ligand dissymmetry of PPz* together with the bipyridine ligand create a "chiral pocket" around the Ru-IV=O moiety, leading to enantiofacial discrimination through nonbonding interaction. Because the acyclic benzylic radical intermediate would undergo cis-trans isomerization before the second C-O bond formation, the overall product enantioselectivity (% ee(obs)) cannot be determined exclusively by facial selectivity (ee(facial)) of the first irreversible C-O bond formation step. The extent of the isomerization, measured by the cis-trans-epoxide selectivity or diastereoselectivity of epoxide ring closure, is an important element in controlling the enantiomeric excess of the epoxides.

  四氧化钌(IV)配合物 [Ru-IV(terpy)(6,6'-Cl-2-bpy)O](ClO4)(2)（1a；terpy = 2,2':6',2"-三联吡啶；6,6'-Cl-2-bpy = 6,6'-二氯-2,2'-联吡啶）、[Ru-IV(terpy)(tmeda)O](ClO4)(2)（1b；tmeda = N,N,N',N'-四甲基乙二胺）、[Ru-IV(Cn)(bpy)O](ClO4)(2)（1c；Cn = 1,4,7-三甲基-1,4,7-三氮杂环壬烷）和 [Ru-IV(PPz*)(bpy)O](ClO4)(2)（1d；PPz* = 2,6-二[(4S,7R)-7,8,8-三甲基-4,5,6,7-四氢-4,7-甲基吲哚唑-2-基]吡啶）在乙腈中于室温条件下有效实现芳香烯的环氧化。它们与顺式烯烃（如顺式-β-甲基苯乙烯和顺式-β-去氘苯乙烯）反应，非立体选择性地生成环氧化物。观察到β-双氘苯乙烯氧化中的逆二级动力学同位素效应（k(H)/k(D) = 0.87（1b）、0.86（1d）），但未在α-对位去氘苯乙烯中观察到（k(H)/k(D) = 0.98，1b和1d），表明C-O键在β-碳的形成比α-碳更进一步，即逐步机制。苯乙烯氧化的二阶速率常数（k(2)）对四氧化钌(IV)配合物的E°(Ru-IV/III)值弱依赖，且电子吸热性和 donating 气对位取代基均轻度加速苯乙烯的氧化反应。这些发现强烈排除了来源于烯烃的阳离子自由基和碳阳离子的中间体。已建立一个线性自由能关系，涉及对位取代苯乙烯氧化的二阶速率常数与总取代基效应（TE）参数：ρ(TE .) = +0.43（R = 0.99）用于1b，+0.50（R = 0.98）用于1c，+0.37（R = 0.99）用于1d（Wu, Y.-D.; Wong, C.-L.; Chan, K. W.; Ji, G.-Z.; Jiang, X.-K. J. Org. Chem. 1996, 61, 746）。这表明，芳香烯通过四氧化钌(IV)配合物的氧化反应应经由苄自由基中间体的速率决定形成步骤。手性四氧化钌(IV)配合物1d对苯乙烯和顺式、反式β-甲基苯乙烯的环氧化实现了中等的对映选择性，其中顺式环氧化物的对映选择性高于反式产物。PPz*配体的不对称性以及联吡啶配体共同在Ru-IV=O基团周围形成一个“手性口袋”，通过非键合相互作用实现对映面分辨。由于无环苄自由基中间体在第二个C-O键形成之前会经历顺式-反式异构化，因此最终产物的对映体选择性（% ee(obs)）不能仅由第一个不可逆C-O键形成步骤的面选择性（ee(facial)）决定。通过顺式-反式环氧化物选择性或反式-反式环氧化物环闭合的对映选择性测量的异构化程度是控制环氧化物中对映体过量的重要因素。