2,2,3,3-tetramethyl-1-tosylaziridine | 432545-79-4

• 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: 2,2,3,3-tetramethyl-1-tosylaziridine
• 英文别名: 2,2,3,3-tetramethyl-N-tosylaziridine；Aziridine, 2,2,3,3-tetramethyl-1-[(4-methylphenyl)sulfonyl]-；2,2,3,3-tetramethyl-1-(4-methylphenyl)sulfonylaziridine
• CAS: 432545-79-4
• 化学式: C₁₃H₁₉NO₂S
• 分子量: 253.365
• InChiKey: OGCWWGXVPOSGRT-UHFFFAOYSA-N

物化性质

• 沸点：
  336.4±35.0 °C(Predicted)
• 密度：
  1.127±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  45.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2,2,3,3-tetramethyl-1-tosylaziridine 在 三氟化硼乙醚 作用下， 以 氯仿 为溶剂， 生成 N-(1,2,2-trimethylpropylidine)-p-toluenesulfonamide
  参考文献：
  名称：

  Aza-pinacol rearrangement: acid-catalyzed rearrangement of aziridines to iminesElectronic supplementary information (ESI) available: experimental procedure and characterization data. See http://www.rsc.org/suppdata/cc/b1/b109445a/

  摘要：

  一系列二取代、三取代和四取代的N-托烯基氮杂环丁烯[N-(托烯基对磺酰基)氮杂环丁烯] 1，通过与N-[(托烯基对磺酰基)-亚胺]苯碘烷(TsN=IPh)反应的氮杂环丁烯合成得到了。结果发现，在温和条件下，这些化合物经过BF3催化的重排（氮杂-pinacol重排）反应，通常能够得到相应的N-托烯基亚胺2，产率令人满意。

  DOI：

  10.1039/b109445a
• 作为产物：
  描述：

  2,3-二甲基-2-丁烯 、 [(N-tosylimino)iodo]benzene 在 {[2.1.1]-(2,6)-pyridinophane}CuCl₂ 、 四(3,5-二(三氟甲基)苯基)硼酸钠 作用下， 以 二氯甲烷 为溶剂， 反应 0.01h， 以98%的产率得到2,2,3,3-tetramethyl-1-tosylaziridine
  参考文献：
  名称：

  角配体约束产生了改进的烯烃叠氮化催化剂。

  摘要：

  [反应：见正文]使用吡啶环，这是一种由三个吡啶组成的大环，通过三个邻位通过CH（2）或CH（2）CH（2）基团与铜结合，产生了良好的性能（速率和产率）催化取代的脂族烯烃和PhINTs转化为氮丙啶。优势还来自使用CH（2）Cl（2）溶剂和弱配位阴离子BAr（4）（-）（Ar = C（6）H（5）或3,5-C（6）H（3） （CF（3））（2））。反应在20摄氏度下仅需数分钟即可完成，对于不带有仲烯丙基CH键的烯烃，其收率几乎是定量的。然而，尽管具有烯丙基氢，但顺式环辛烯仅产生氮丙啶。

  DOI：

  10.1021/ol034681p

文献信息

• An Electron-Poor Dioxa-[2.1.1]-(2,6)-pyridinophane Ligand and Its Application in Cu-Catalyzed Olefin Aziridination
  作者：Fan Yang、Jiaheng Ruan、Peter Y. Zavalij、Andrei N. Vedernikov

  DOI：10.1021/acs.inorgchem.9b02618

  日期：2019.11.18

  fluxional at 20 °C. In the crystalline copper(I) complex LCuCl, the macrocyclic ligand is also κ2-N,N-coordinated to the metal, but it utilizes two equivalent pyridine fragments for the binding. The copper(I) complex is fluxional in CH2Cl2 solutions in the temperature range between 20 and −70 °C and is proposed to be involved in a fast intermolecular macrocyclic ligand exchange which is slowed down

  合成了一种新型的大环1,7-二氧杂-[2.1.1]-（2,6）-吡啶并ligand烷配体，并进行了晶体学表征。制备了两种衍生的金属配合物，二氯钯（II）和氯铜（I）。在钯（II）配合物LPdCl 2中，根据其晶体学特征，无论是固态的，还是在−40°C的CH 2 Cl 2溶液中，根据1 H NMR光谱，配体均适应于C 1-对称的κ 2 - ñ，ñ金属原子与大环的两个非等价吡啶片段结合的-配位模式。该络合物在20°C时具有通量。在结晶铜（I）络合物LCuCl，所述大环配位体也是κ 2 - Ñ，Ñ配位的对金属，但它采用了两个当量吡啶片段用于结合。铜（I）配合物在20至-70°C的温度范围内在CH 2 Cl 2溶液中呈熔体流动，并被提议参与快速的分子间大环配体交换，而交换速度低于-40°C。DFT计算预测，二氧杂吡啶并吡啶并环的化合物LPdCl 2的热力学稳定性较低。与LCuCl和LCuCl相比，它们的[2
• A Practical, Fast, and High-Yielding Aziridination Procedure Using Simple Cu(II) Complexes Containing N-Donor Pyridine-Based Ligands
  作者：Fabian Mohr、Seth A. Binfield、James C. Fettinger、Andrei N. Vedernikov

  DOI：10.1021/jo050485f

  日期：2005.6.1

  tetramethylethylene. For cis-cyclooctene, indene, methyl acrylate, methyl methacrylate, vinyl methyl ketone, tert-butylethylene, and neopentylethylene, as well as for 1-hexene and cyclopentene, yields of corresponding aziridines vary from 44% to 83%. The catalytic activity and efficiency of the reported copper complexes decrease moderately in the absence of NaBArF4.

  衍生自二（2-吡啶基）甲烷或吡啶本身的四配位二氯铜（II）配合物在弱配位氯仿中，在存在1-2当量的NaBAr F 4（BAr F 4 - =四[3,5-二（三氟甲基）苯基]硼酸盐）。对于诸如苯乙烯，三和四甲基乙烯这样的反应性烯烃，以1：1的烯烃/ PhINTs比和1-5摩尔％的催化剂负载量，可以获得超过90％的高氮丙啶收率。用于顺式环辛烯，茚，丙烯酸甲酯，甲基丙烯酸甲酯，乙烯基甲基酮，叔丁基丁基乙烯和新戊基乙烯，以及1-己烯和环戊烯的相应氮丙啶的收率从44％到83％不等。在没有NaBAr F 4的情况下，所报道的铜配合物的催化活性和效率适度降低。
• Cationic Divalent Metal Sites (M = Mn, Fe, Co) Operating as Both Nitrene-Transfer Agents and Lewis Acids toward Mediating the Synthesis of Three- and Five-Membered<i>N</i>-Heterocycles
  作者：Suraj Kumar Sahoo、Brent Harfmann、Lin Ai、Qiuwen Wang、Sudip Mohapatra、Amitava Choudhury、Pericles Stavropoulos

  DOI：10.1021/acs.inorgchem.3c01209

  日期：2023.7.10

  practicable yields, involving a single-pot cycloaddition reaction of alkene, nitrene, and ketone (2 + 1 + 2). Mechanistic studies indicate that the most productive bipodal Fe(II) site mediates stepwise addition of nitrene to olefins to generate aziridines with good retention of stereochemistry and further enables aziridine ring opening to unmask a 1,3-zwitterion that can undergo cycloaddition with dipolarophiles

  三足化合物 [（TMG3trphen）MII–solv]（PF6）2 （M = Mn， Fe， Co;solv = MeCN， DMF） 和两足类似物 [（TMG2biphen）MII（NCMe）x]（PF6）2 （x = 3 for Mn， Fe;x = 2 for Co） 和 [（TMG2biphen）MIICl2] 是用具有三芳基或二芳基甲基胺框架和超碱性四甲基胍基残基 （TMG） 的配体合成的。在乙基氮中，二元 M（II） 位点介导亚胺二烷 PhI═NTs（Ts = 甲苯磺酰基）和一组苯乙烯之间的催化硝酰转移反应，以提供氮丙啶和咪唑啉的低产率（在 MeCN 插入时），其生产率顺序有利于双足细胞而不是三足体试剂，金属偏好 Fe > Co ≥ Mn。在 CH2Cl2 中，酸性更强的 Fe（II） 位点有利于通过最初生成的 2-芳基-N-甲苯磺酰丙啶与残留苯乙烯的原位 （3 + 2） 环加成反应形成
• Syntheses of acetonitrile ligated copper complexes with perfluoroalkoxy aluminate as counter anion and their catalytic application for olefin aziridination
  作者：Yang Li、Bernd Diebl、Alexander Raith、Fritz E. Kühn

  DOI：10.1016/j.tetlet.2008.07.162

  日期：2008.10

  Acetonitrile ligated copper complexes with perfluoroalkoxy aluminate Al OC(CF3)(3)}(4)(-), as weakly coordinating counter anion are successfully synthesized. Aziridination of various olefins with PhlNTs catalyzed by copper(II) complex [Cu(II)(NCCH3)(6)][AlOC(CF3)(3}4)](2) affords good to excellent yields (up to 96%) and very high turnover frequency (higher than 5000 h(-1)) under mild conditions. (C) 2008 Elsevier Ltd. All rights reserved.
• Aziridination of Alkenes and Amidation of Alkanes by Bis(tosylimido)ruthenium(VI) Porphyrins. A Mechanistic Study
  作者：Sze-Man Au、Jie-Sheng Huang、Wing-Yiu Yu、Wai-Hong Fung、Chi-Ming Che

  DOI：10.1021/ja9913481

  日期：1999.10.1

  Bis(tosylimido)ruthenium(VI) porphyrins, [Ru-VI(Por)(NTs)(2)] (Por TPP. TTP 4-Cl-TPP 4-MeO-TPP. OEP), were prepared in 60-74% yields by treatment of [Ru-II(Por)(CO)(MeOH)] with (N-(p-tolylsulfonyl)imino)phenyliodinane (PhI=NTs) in dichloromethane. In dichloromethane containing pyrazole, they reacted with alkenes or alkanes to give tosylamidoruthenium(IV) porphyrins, [Ru-IV(Por)(NHTs)(pz)], in about 75% yields. The reactions of [Ru-VI(TPP)(NTs)(2)] and [Ru-VI(OEP)(NTs)(2)] with styrene, para-substituted styrenes, norbornene, cyclooctene, and beta-methylstyrene afforded the corresponding N-tosylaziridines in 66-85% yields. The aziridination of cis-stilbene and cis-beta-methylstyrene by [Ru-VI(Por)(NTs)(2)] is nonstereospecific with a partial loss of the alkene stereochemistry. Kinetic studies on the reactions between [Ru-VI(TPP)(NTs)(2)] and 16 alkenes (cyclooctene, norbornene, 2,3-dimethyl-2-butene, styrene, para-substituted styrenes, alpha- and beta-methylstyrene, and alpha- and beta-deuteriostyrene) gave the second-order rate constants (k(2)) ranging from (1.60 +/- 0.06) x 10(-3) to (90 +/- 4) x 10(-3) dm(3) mol(-1) s(-1) at 298 K. The slope of the linear plot of log k(2) vs E-1/2 for eight representative alkenes was found to be -1.7 V-1. Tn the case of para-substituted styrenes, linear correlation between log k(R) (k(R) = relative rate) and sigma(+) gives a rho(+) value as small as -1.1. However, the effect of para substituents on k(R) can be best accounted for by considering both the polar and spin delocalization effect. Measurements on the secondary deuterium isotope effect revealed that only the beta-carbon atom of styrene experienced a significant change in its hybridization in reaching the transition state. All these are consistent with rate-determining formation of a carboradical intermediate. The reactions of [Ru-VI(TPP)(NTs)(2)] and [Ru-VI(OEP)(NTs)(2)] with adamantane, cyclohexene, ethylbenzene, and cumene resulted in tosylamidation of these hydrocarbons and afforded the corresponding amides in 52-88% yields. For cyclohexane and toluene, the tosylamidation products were formed in poor yields (ca. 10%). Kinetic studies on the reactions between [Ru-VI(TPP)(NTs)(2)] and nine hydrocarbons (cumene, ethylbenzene, cyclohexene, and para-substituted ethylbenzenes) gave the second-order rate constants (k(2)) in the range of (0.330 +/- 0.008) x 10(-3) to (16.5 +/- 0.3) x 10(-3) dm(3) mol(-1) s(-1). These reactions exhibit a large primary deuterium isotope effect, with a k(H)/k(D) ratio of 11 for the tosylamidation of ethylbenzene. In the case of para-substituted ethylbenzenes, both electron-donating and -withdrawing substituents moderately promote the reaction. There is an excellent linear correlation between log k(R) and a related carboradical parameter. On the basis of these observations, a mechanism involving the rate-limiting formation of a carboradical intermediate is postulated.