(2S,3S)-2-(4-nitrophenyl)-3-phenyl oxirane | 14985-26-3

• 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: (2S,3S)-2-(4-nitrophenyl)-3-phenyl oxirane
• 英文别名: trans-4-Nitrostilbene oxide；(2S,3S)-2-(4-nitrophenyl)-3-phenyloxirane
• CAS: 14985-26-3
• 化学式: C₁₄H₁₁NO₃
• 分子量: 241.246
• InChiKey: YUZKNYLREGXARL-KBPBESRZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  58.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  (1S,4S,5S,6S)-6-benzyl-4,7,7-trimethyl-6-thioniabicyclo[3.2.1]octane trifluoromethanesulfonate 、 对硝基苯甲醛 在 potassium hydroxide 作用下， 以 乙腈 为溶剂， 生成 (2S,3S)-2-(4-nitrophenyl)-3-phenyl oxirane
  参考文献：
  名称：

  A mild access to chiral syn 1,2-diaryl glycols by stereoselective ring opening of ortho substituted trans 2,3-diaryl-oxiranes using Amberlyst 15 in H2O/THF system

  摘要：

  Amberlyst 15 was an efficient and green catalyst for the reaction of 2,3-diaryloxiranes with H2O in organic co-solvent to prepare glycols in high yield. Ortho substituted trans 2,3-diaryloxiranes afforded the corresponding syn glycols stereo- and enantiospecifically. Stereoselectivity appeared related to the coordination ability of the substituents, irrespective of their electronic properties. Indeed o-OCH3 and o-OBn substituted syn glycols were obtained in high stereochemical ratios (6/1 and 10/1, respectively), and o-OTIPS and o-NO2 substituted ones were obtained as exclusive products, with the same ee of the parent epoxides. (C) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2015.06.039

文献信息

• A New Protocol for the In Situ Generation of Aromatic, Heteroaromatic, and Unsaturated Diazo Compounds and Its Application in Catalytic and Asymmetric Epoxidation of Carbonyl Compounds. Extensive Studies To Map Out Scope and Limitations, and Rationalization of Diastereo- and Enantioselectivities
  作者：Varinder K. Aggarwal、Emma Alonso、Imhyuck Bae、George Hynd、Kevin M. Lydon、Matthew J. Palmer、Mamta Patel、Marina Porcelloni、Jeffery Richardson、Rachel A. Stenson、John R. Studley、Jean-Luc Vasse、Caroline L. Winn

  DOI：10.1021/ja034606+

  日期：2003.9.1

  a general process for the in situ generation of diazo compounds from tosylhydrazone sodium salts has been established and applied in sulfur-ylide mediated epoxidation reactions. The chiral, camphor-derived, [2.2.1] bicyclic sulfide 7 was employed (at 5-20 mol % loading) to render the above processes asymmetric with a range of carbonyl compounds and tosylhydrazone sodium salts. Benzaldehyde tosylhydrazone

  已经制备了多种衍生自苯甲醛的金属化甲苯磺酰腙盐，并在四氢噻吩 (THT) (20 mol %) 和 Rh(2)(OAc)(4) (1 mol %) 存在下与苯甲醛反应，得到二氧化二苯乙烯. 在所测试的锂盐、钠盐和钾盐中，发现钠盐的产率和选择性最高。该研究扩展到各种芳香族、杂芳香族、脂肪族、α、β-不饱和和乙炔醛以及酮。总的来说，观察到具有中等至非常高的非对映选择性的环氧化物的高产率。还使用相同的方案在与苯甲醛的反应中检查了衍生自芳香族、杂芳香族和 α,β-不饱和醛的范围广泛的甲苯磺酰腙盐，再次，在大多数情况下观察到良好的产率和高的非对映选择性。因此，已经建立了从甲苯磺酰腙钠盐原位生成重氮化合物的一般方法，并将其应用于硫-叶立德介导的环氧化反应。使用手性、樟脑衍生的 [2.2.1] 双环硫化物 7（以 5-20 mol% 负载量）使上述过程与一系列羰基化合物和甲苯磺酰腙钠盐不对称。苯甲醛甲苯磺酰腙钠盐提供
• Catalytic Asymmetric Synthesis of Epoxides from Aldehydes Using Sulfur Ylides with In Situ Generation of Diazocompounds
  作者：Varinder K. Aggarwal、Emma Alonso、George Hynd、Kevin M. Lydon、Matthew J. Palmer、Marina Porcelloni、John R. Studley

  DOI：10.1002/1521-3773(20010417)40:8<1430::aid-anie1430>3.0.co;2-w

  日期：2001.4.17

  absolute stereochemistry has been achieved by generating the reactive intermediate (the diazo compound) in situ from tosylhydrazone salts (see scheme, PTC=phase-transfer catalyst, Ts=toluene-4-sulfonyl). High yields (58-82 %), high d.r. (88:12-98:2), and high ee values (87-94 %) have been obtained using a new class of stable chiral sulfides at low catalyst loading (5 mol %) and [Rh2 (OAc)4 ] (0.5 mol %).

  通过从甲苯磺酰salts盐原位生成反应性中间体（重氮化合物），已实现了控制相对和绝对立体化学的实用，通用且收敛的环氧化物途径（参见方案，PTC =相转移催化剂，Ts =甲苯） -4-磺酰基）。使用新型的稳定的手性硫化物，在低催化剂负载量（5 mol％）下，已获得高产率（58-82％），高dr（88：12-98：2）和高ee值（87-94％） ）和[Rh 2（OAc）4 ]（0.5摩尔％）。
• Experimental Evidence for Multiple Oxidation Pathways in the (salen)Mn-Catalyzed Epoxidation of Alkenes
  作者：Christian Linde、Nordine Koliaï、Per-Ola Norrby、Björn Åkermark

  DOI：10.1002/1521-3765(20020603)8:11<2568::aid-chem2568>3.0.co;2-z

  日期：2002.6.3

  the catalytic epoxidation of para-substituted cis stilbenes 2a-i were investigated by using (R,R)-[N,N'-bis(3,5-di-tBu-salicylidene)-1,2-cyclohexanediamine]manganese(III) chloride 1 in benzene as the catalyst with iodosobenzene as the terminal oxidant. A Hammett study of the selectivity results reveals a stronger electrophilic character than previously assumed in the (salen)Mn-catalyzed reaction. In

  使用（R，R）-[N，N'-bis（3,5-di-tBu-Salicylidene）-1研究了底物电子对对位取代的顺式斯蒂尔苯酯2a-i催化环氧化反应选择性的影响1,2-环己烷二胺]氯化锰（III）1在苯中作为催化剂，碘代苯作为末端氧化剂。Hammett对选择性结果的研究表明，其亲电特性比以前在（salen）Mn催化的反应中所假定的要强。通常，通过使用Hammett sigma +值获得与实验值的最佳相关性，对于顺式环氧形成速率，rho = -1.37；对于逐步反应的逐步过程速率，rho = -0.43。反产品。该反应涉及两个单独的途径，这也由中间体在甲氧基取代的底物的反式环氧化物的竞争性竞争中表明。对于4-甲氧基-4'-亚硝基二苯乙烯而言，导致顺式环氧化物的协同途径中的异步性是显而易见的，由于电子效应，其完全产生具有75％ee的顺式环氧化物。
• 3- and 4-Uloses Derived from N-Acetyl-D-glucosamine: A Unique Pair of Complementary Organocatalysts for Asymmetric Epoxidation of Alkenes
  作者：Christof Schöberl、Volker Jäger

  DOI：10.1002/adsc.201100735

  日期：2012.3.16

  The 4‐ulose and the 3‐ulose, both derived in two steps from the α‐methyl glycoside of N‐acetyl‐D‐glucosamine (GlcNAc), act as organocatalysts in the asymmetric epoxidation of alkenes, with unprecedented complementary enantioselectivity. The best results are found with α,β‐unsaturated esters as substrates, with enantiomeric ratios up to 90:10 and 11:89, respectively.

  N-乙酰基-D-葡糖胺（GlcNAc）的α-甲基糖苷（GlcNAc）分两步衍生出来的4-ulose和3-ulose在烯烃的不对称环氧化中起有机催化剂的作用，具有前所未有的互补对映选择性。以α，β-不饱和酯为底物发现最佳结果，对映体比例分别高达90:10和11:89。
• Preparation of a novel, camphor-derived sulfide and its evaluation as a chiral auxiliary mediator in asymmetric epoxidation via the Corey–Chaykovsky reaction
  作者：Takao Saito、Daisuke Akiba、Masao Sakairi、Shintaro Kanazawa

  DOI：10.1016/s0040-4039(00)01878-5

  日期：2001.1

  Sulfonium ylide-mediated asymmetric one-pot synthesis of optically active epoxides from aldehydes and bromides via the Corey–Chaykovsky reaction is described. The optically pure chiral sulfide was readily prepared from natural camphor via thiabutadiene Diels–Alder cycloaddition, followed by LiAlH4 reduction and hydrogenation of the cycloadduct.

  叙述了通过Corey-Chaykovsky反应由乙醛和溴化物介导的叶立德介导的不对称一锅合成光学活性环氧化物。光学纯的手性硫化物很容易从天然樟脑中经硫代丁二烯Diels–Alder环加成制备，然后进行LiAlH 4还原和加成环加氢。