1-benzyl-2-vinylaziridine | 202596-67-6

• 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: 1-benzyl-2-vinylaziridine
• 英文别名: N-benzyl-2-vinylaziridine；Vinylbenzylaziridine；1-benzyl-2-ethenylaziridine
• CAS: 202596-67-6
• 化学式: C₁₁H₁₃N
• 分子量: 159.231
• InChiKey: VZNVWCSXXYJGLP-UHFFFAOYSA-N

物化性质

• 沸点：
  208.0±29.0 °C(Predicted)
• 密度：
  1.109±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-benzyl-2-vinylaziridine 在 zirconocene hydrochloride 作用下， 以 二氯甲烷 为溶剂， 反应 2.5h， 以86%的产率得到N-苄基(环丙基)甲胺
  参考文献：
  名称：

  Hydrozirconation of alkenyloxirane derivatives: Preparation of cycloalkylmethanols

  摘要：

  Cyclopentyl and cyclopropylmethanol derivatives were efficiently prepared through a chemoselective hydrozirconation reaction of (1-butenyl)oxirane and vinyloxirane with Cp2ZrHCl. However, the attemped reaction of (1-pentenyl)oxirane or (1-propenyl)oxirane failed to yield cyclohexyl or cyclobutylmethanols. The ring formation was stereospecific and proceeded with the inversion of the configuration at the reacting oxirane carbon. The origin of stereospecificity and the stereoselectivity in the formation of cyclopropylmethanols was presumed by the approach of the Schwartz reagent from the less hindered site of the stable gauche-conformer of the vinyloxirane compound in the transition state. (Cyclopropylmethyl)amine derivatives were also prepared by the treatment of vinylaziridine derivatives with Cp2ZrHCl. (C) 1997 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(97)10340-4
• 作为产物：
  描述：

  在 sodium tetrahydroborate 、 triphenylphosphine dibromide 1:1 addition complex 、 N,N-二异丙基乙胺 作用下， 以 甲醇 、 乙腈 为溶剂， 反应 21.0h， 生成 1-benzyl-2-vinylaziridine
  参考文献：
  名称：

  Dynamic Kinetic Asymmetric Cycloadditions of Isocyanates to Vinylaziridines

  摘要：

  The first examples of the use of racemic vinylaziridines in a Pd-catalyzed dynamic kinetic asymmetric transformation have been examined. Optimization studies of the Pd-catalyzed addition of vinylaziridines to isocyanates revealed that the chiral ligand between trans-1,2-diaminocyclohexane and 2-diphenylphosphino-1-naphthoic acid is superior to that involving 2-diphenylphosphino benzoic acid. Surprisingly, high ee's required the use of an acid whose pKa was about 4.7 +/- 0.1 as a cocatalyst. Both acetic acid and hydroxybenzotriazole meet this requirement. Less electrophilic isocyanates (e.g., benzyl, p-methoxyphenyl) gave higher ee's than more electrophilic ones (phenyl or benzoyl). Both N-benzyl and N-arylaziridines react well to give good yields and ee's, whereas N-tosylaziridines gave lower ee's. A 1,1-disubstituted aziridine led to the formation of a tertiary C-N bond with ee's comparable to the formation of the secondary C-N bond. The products were easily reduced almost quantitatively to the sensitive imidazolidines which can be readily hydrolyzed to the vicinal diamines. The reactivity pattern is consistent with a Curtin-Hammett situation wherein the enantiodiscriminating event is the cyclization of a rapidly equilibrating dynamic pi-allyl palladium intermediate.

  DOI：

  10.1021/ja037450m

文献信息

• [5 + 2] Cycloaddition Reaction of 2-Vinylaziridines and Sulfonyl Isocyanates. Synthesis of Seven-Membered Cyclic Ureas
  作者：Eri Kanno、Kenichi Yamanoi、Shunsuke Koya、Isao Azumaya、Hyuma Masu、Ryu Yamasaki、Shinichi Saito

  DOI：10.1021/jo201959a

  日期：2012.3.2

  The [5 + 2] cycloaddition reaction of 2-vinylaziridines with sulfonyl isocyanates proceeded smoothly under mild conditions, and various cyclic ureas were isolated in high yields. The remarkable solvent effect on the reaction was observed, and the preferential formation of the seven-membered ring occurred when the reaction was carried out in CH2Cl2. The scope and limitation were studied, and the mechanism

  2-乙烯基氮丙啶与磺酰基异氰酸酯的[5 + 2]环加成反应在温和条件下平稳进行，并以高收率分离出各种环状脲。观察到对反应的显着溶剂作用，并且当在CH 2 Cl 2中进行反应时，优先形成了七元环。研究了反应的范围和局限性，并讨论了该反应的机理。本研究为合成七元环脲提供了一种新的简单方法。
• Palladium-Catalyzed Dynamic Kinetic Asymmetric Transformations of Vinyl Aziridines with Nitrogen Heterocycles: Rapid Access to Biologically Active Pyrroles and Indoles
  作者：Barry M. Trost、Maksim Osipov、Guangbin Dong

  DOI：10.1021/ja1071509

  日期：2010.11.10

  heterocycles can serve as competent nucleophiles in the palladium-catalyzed dynamic kinetic asymmetric alkylation of vinyl aziridines. The resulting alkylated products were obtained with high regio-, chemo-, and enantioselectivity. Both substituted 1H-pyrroles and 1H-indoles were successfully employed to give exclusively the branched N-alkylated products. The synthetic utility of this process was demonstrated

  我们报告说，氮杂环可以在钯催化的乙烯基氮丙啶动态动力学不对称烷基化中作为有能力的亲核试剂。得到的烷基化产物具有高区域选择性、化学选择性和对映选择性。取代的 1H-吡咯和 1H-吲哚都被成功地用于得到支化的 N-烷基化产物。通过将该方法应用于制备几种药物化学先导化合物和溴吡咯生物碱，包括 longamide B、longamide B 甲酯、hanishin、agesamides A 和 B 以及环碘酮，证明了该方法的合成效用。
• Synergistic Catalysis for the Asymmetric [3+2] Cycloaddition of Vinyl Aziridines with α,β-Unsaturated Aldehydes
  作者：Line Naesborg、Fernando Tur、Marta Meazza、Jakob Blom、Kim Søholm Halskov、Karl Anker Jørgensen

  DOI：10.1002/chem.201604995

  日期：2017.1.5

  The first asymmetric [3+2] cycloaddition of vinyl aziridines with α,β‐unsaturated aldehydes, based on synergistic catalysis, is disclosed. This methodology allows the formation of attractive pyrrolidine structures in good yields (up to 84 %), moderate diastereoselectivity, and high enantioselectivity values (up to >99 % ee). Additionally, a tricyclic pyrrolidine core structure found in biologically

  公开了基于协同催化的乙烯基氮丙啶与α，β-不饱和醛的第一次不对称[3 + 2]环加成反应。这种方法可以以高收率（高达84％），中等非对映选择性和高对映选择性（高达> 99％ee）形成有吸引力的吡咯烷结构。此外，使用提出的反应概念以一锅法合成了在生物活性分子中发现的三环吡咯烷核心结构。最后，概述了机械方案。
• The Photochemical Reaction of Vinylaziridines and Vinylazetidines with Chromium(0) and Molybdenum(0) (Fischer) Carbene Complexes
  作者：Alexandra R. Rivero、Israel Fernández、Miguel A. Sierra

  DOI：10.1002/chem.201302029

  日期：2014.1.27

  The [5+2] and [6+2] cycloaddition reactions of vinylaziridines and vinylazetidines with ketenes generated photochemically from chromium(0) and molybdenum(0) Fischer carbene complexes have been investigated. These processes constitute a straightforward and efficient route to azepanones and azocinones, respectively. The peculiar electronic properties of the metalated ketenes allow for the introduction

  已研究了乙烯基氮丙啶和乙烯基氮杂环丁烷与由铬（0）和钼（0）菲舍尔卡宾络合物光化学生成的烯酮的[5 + 2]和[6 + 2]环加成反应。这些方法分别构成了直接获得氮杂环丁烷酮和偶氮醌的途径。金属化的烯酮具有独特的电子性能，可以在最终的环加合物中引入富电子的取代基，这是使用常规有机化学方法的一项艰巨任务。通过使用Cr 0证明了该工艺的多功能性费歇尔双（卡宾）络合物作为金属化的双（酮）前体。这些物质在温和的反应条件下，一步即可生成束缚的双（氮杂环庚烷）。密度泛函理论计算指出，通过氮丙啶氮原子在金属化乙烯酮上的最初亲核进攻，然后是形成的两性离子中间体的闭环，逐步形成了反应路径。
• Metal-free aza-Claisen type ring expansion of vinyl aziridines: an expeditious synthesis of seven membered N-heterocycles
  作者：Deepak Singh、Hyun-Joon Ha

  DOI：10.1039/c8ob03029d

  日期：——

  A metal-free approach for the synthesis of 7-membered aza-heterocycles has been developed by the intermolecular [5 + 2] cycloaddition of non-activated vinylaziridines and alkynes. This method has a broad substrate scope under mild reaction conditions to afford structurally diverse 7-membered N-heterocycles in high yield up to 92%.

  通过非活化的乙烯基氮丙啶和炔烃的分子间[5 + 2]环加成反应，已经开发出了一种无金属合成7元氮杂杂环的方法。该方法在温和的反应条件下具有较宽的底物范围，可以以高达92％的高收率提供结构多样的7元N-杂环。