cis-β-deuterio-styrene oxide | 29430-01-1

• 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: cis-β-deuterio-styrene oxide
• 英文别名: cis-β-deuteriostyrene oxide；(Z)-1-deuterostyrene oxide；(2S,3R)-2-deuterio-3-phenyloxirane
• CAS: 29430-01-1；101977-04-2；101977-05-3；108645-29-0；119365-75-2
• 化学式: C₈H₈O
• 分子量: 121.143
• InChiKey: AWMVMTVKBNGEAK-JZRNAXLVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  9
• 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：
  1

反应信息

• 作为反应物：
  描述：

  cis-β-deuterio-styrene oxide 在 [Ru(N,N'-ethylenebis(salicylideneaminate)(NO)(H2O)](SbF6) 、 硫酸 、 potassium thioacyanate 作用下， 以 1,4-二氧六环 、 硝基甲烷-d3 为溶剂， 反应 36.0h， 生成 (Z)-styrene-β-d
  参考文献：
  名称：

  钌Salen亚硝基配合物催化硫丙烷合成三硫戊环和四硫烷

  摘要：

  化合物 [Ru(salen)(NO)(H(2)O)](SbF(6)) (1)（salen = N,N'-亚乙基-双-水杨基胺）与硫杂丙烷催化反应并将它们转化为烯烃和 1,2,3,4-四硫杂环烷或 1,2,3-三硫杂环戊烷。单取代硫杂丙环硫醚和硫化丙烯反应生成相应的烯烃和 4-取代的 1,2,3-三硫杂环戊烷，其比例为 2:1，分离产率超过 90%。在催化量 1 的 CD(3)NO 存在下，二取代硫杂丙烷顺式二苯乙烯硫醚以 3:1 的比例转化为顺式二苯乙烯和 5,6-反式-1,2,3,4-二苯基四硫烷(2). 通过分离 [Ru(salen)(NO)(cis-stilbene sulfide)](SbF(6)) (6)，建立了在配体取代反应中顺式二苯乙烯硫化物与 salen 复合物的协调。(1) 对 6 进行的 H NMR 研究表明，salen 大环已在硫杂环丙烷配位后重新排列。发现类似的重排

  DOI：

  10.1021/ja017462c
• 作为产物：
  描述：

  苯乙炔-d 在 5,10,15,20-tetrakis(pentafluorophenyl)-21H,23H-porphyrin iron(III) chloride 9-borabicyclo[3.3.1]nonane dimer 、 lithium hypochlorite 、 1,2,3,4,5-pentafluoro-6-iodosylbenzene 、 溶剂黄146 作用下， 以 二氯甲烷 为溶剂， 反应 27.0h， 生成 cis-β-deuterio-styrene oxide
  参考文献：
  名称：

  通过细胞色素 P-450 模型系统对苯乙烯进行氧化。机理研究

  摘要：

  L'oxydation du 苯乙烯, catalysee par des porphyrines de Fe ou de Mn, 导管 a du 苯乙醛 a cote de l'epoxyde escompte。On Demontre que l'aldehyde est le produit primaire et qu'il ne resulte pas de l'isomerisation de l'oxyde de 苯乙烯。Marquage isotopique au deuterium

  DOI：

  10.1021/ja00270a016

文献信息

• Zinc(<scp>II</scp>)-catalysed transformation of epoxides to aziridines
  作者：Dorte Kühnau、Ib Thomsen、Karl Anker Jørgensen

  DOI：10.1039/p19960001167

  日期：——

  The Lewis acid-catalysed transformation of epoxides to aziridines with iminophosphoranes as the nitrogen-fragment donor has been investigated. Of the Lewis acids tested, zinc(II) complexes had the best catalytic properties. The method works best for terminal and cyclic epoxides, internal epoxides being less reactive. Of the various iminophosphoranes employed N-(triphenylphosphoranylidene)-aniline and

  已经研究了路易斯酸催化的以亚氨基正膦为氮片段供体的环氧化物向氮丙啶的转化。在测试的路易斯酸中，锌（II）配合物具有最佳的催化性能。该方法最适用于末端和环状环氧化物，内部环氧化物的反应性较低。在使用的各种亚氨基正膦中，最成功的是N-（三苯基正膦亚基）-苯胺和-异丙胺。对于手性苯乙烯氧化物，已经研究了锌（II）催化的反应，对于该手性氧化苯乙烯，所生成的氮丙啶的对映体过量取决于反应时间。非手性和手性氧化苯乙烯与N-（三苯基磷酰亚烷基）苯胺在锌（为了获得有关反应的立体化学结果的信息，已经研究了具有手性配体的II）配合物，以及针对顺式-氘代环氧乙烷的反应。根据实验结果讨论了标题反应的机理。
• 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。
• Ruthenium <i>meso</i>-Tetrakis(2,6-dichlorophenyl)porphyrin Complex Immobilized in Mesoporous MCM-41 as a Heterogeneous Catalyst for Selective Alkene Epoxidations
  作者：Chun-Jing Liu、Wing-Yiu Yu、Shou-Gui Li、Chi-Ming Che

  DOI：10.1021/jo981003l

  日期：1998.10.1

  A ruthenium complex of meso-tetrakis(2,6-dichlorophenyl)porphyrin, [Ru(II)(TDCPP)(CO)(EtOH)], is immobilized into mesoporous MCM-41 molecular sieves; the supported Ru catalyst can effect highly selective heterogeneous alkene epoxidations using 2,6-dichloropyridine N-oxide as terminal oxidant. Aromatic and aliphatic alkenes can be efficiently converted to their epoxides in good yields and selectivities

  将介孔四（2,6-二氯苯基）卟啉的钌络合物[Ru（II）（TDCPP）（CO）（EtOH）]固定在介孔MCM-41分子筛中；使用2,6-二氯吡啶N-氧化物作为末端氧化剂，负载型Ru催化剂可以实现高度选择性的异质烯烃环氧化。芳族和脂族烯烃可以有效地以良好的收率和选择性有效地转化为其环氧化物，而顺式烯烃，例如顺式-苯乙烯，顺式-β-甲基苯乙烯和顺式-β-氘代苯乙烯被立体定向​​地环氧化。环烯（如降冰片烯和环辛烯）的氧化可使用非均相Ru催化反应有效地进行，而这些烯烃在沸石基硅酸钛（TS-1）催化的条件下不发生反应（Murugavel，R .; Roesky， HW Angew.Chem。，Int.Ed.Engl.1997，36，477）。另一方面，Ru / M-41（m）催化剂在（+）-柠檬烯氧化中显示出尺寸选择性，其中末端C ＝ C键（相对于内部三取代的C ＝ C键）变得更容易被氧化。庞大的3
• A Mechanistic Investigation of Alkene Epoxidation by Sterically Encumbered <i>trans</i>-Dioxoruthenium(VI) Porphyrins
  作者：Chun-Jin Liu、Wing-Yiu Yu、Chi-Ming Che、Chi-Hung Yeung

  DOI：10.1021/jo990517x

  日期：1999.10.1

  The highly substituted dioxoruthenium(VI) porphyrins [Ru-VI(DPP)O-2] (1a; H2DPP = 2,3,5,7,8;10,- 12,13,15,17, 18,20-dodecaphenylporphyrin), [Ru-VI(TDCPP)O-2] (Ib; H2TDCPP = meso-tetrakis(2,6- dichlorophenyl)porphyrin), and [Ru-VI(TMOPP)O-2] (1c; H2TMOPP = meso-tetrakis(2,4,6-trimethoxyphenyl)porphyrin) are competent oxidants for alkene epoxidation. The oxidations were carried out in a CH2Cl2/Hpz solution, and a paramagnetic bis(pyrazolato)ruthenium(IV) porphyrin, [Ru-IV(Por)-(pz)(2)] (2; H(2)Por = H2DPP, H2TDCPP, H2TMOPP), was isolated and characterized. For the oxidation of cis-alkenes, stereoselectivity is dependent upon both the alkenes and the ruthenium oxidants, and it decreases in the order: cis-stilbene > cis-beta-methylstyrene > cis-beta-deuteriostyrene. The observation of inverse secondary KIE for the oxidation of beta-d(2)-styrene [k(H)/k(D) = 0.87 (1a); 0.86 (1b)] but not for the alpha-deuteriostyrene oxidations suggests that the C-O bond formation is more advanced at the C(beta) atom than at the C(alpha) atom of styrene, consistent with a nonconcerted mechanism. By consideration of spin delocalization and polar effects, the second-order rate constants for the oxidation of para-substituted styrenes by complexes la-c can linearly correlate with the carboradical substituent constants sigma(mb) and sigma(JJ)(.) (Jiang, X.-K. Acc. Chem. Res. 1997, 30, 283). This implies that the styrene oxidation by the dioxoruthenium(VI) porphyrins should involve rate-limiting generation of a benzylic radical intermediate, and the magnitude of \rho(JJ)(.)\rho(mb)\ > 1 suggests that the spin delocalization effect is more important than the polar effect in the epoxidation reactions. The spontaneous epoxidation of trans-beta-methylstyrene by the sterically encumbered [Ru-VI(TDCPP)O-2] and [Ru-VI(TMOPP)O-2] complexes and the comparable Delta S-double dagger values for their reactions with trans-beta-methylstyrene and styrene are incompatible with the "side-on approach" model; a "head-on approach" model is implicated.
• Diastereotopic selection of C2 hydrogens in the rearrangement of C1-substituted epoxides: An examination of styrene oxide
  作者：J.M. Coxon、D.Q. McDonald

  DOI：10.1016/s0040-4039(00)86115-8

  日期：1988.1