tert-butyl (1S,4R)-2-oxa-3-aza-bicyclo-[2,2,2]oct-5-ene-3-carboxylate | 266306-65-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 恶嗪烷类
• 英文名称: tert-butyl (1S,4R)-2-oxa-3-aza-bicyclo-[2,2,2]oct-5-ene-3-carboxylate
• 英文别名: (-)-t-Butyl (1S,4R)-2-oxa-3-azabicyclo[2.2.2]oct-5-ene-3-carboxylate；tert-butyl 2-oxa-3-azabicyclo[2.2.2]oct-5-ene-3-carboxylate；N-tert-Butyloxycarbonyl-3-aza-2-oxabicyclo[2.2.2]oct-5-ene；N-tert-butoxycarbonyl-2-oxa-3-azabicyclo[2.2.1]oct-5-ene；tert-butyl 2-aza-3-oxabicyclo[2.2.2]oct-5-ene-2-carboxylate；tert-butyl (1S,4R)-2-oxa-3-azabicyclo[2.2.2]oct-5-ene-3-carboxylate
• CAS: 266306-65-4
• 化学式: C₁₁H₁₇NO₃
• 分子量: 211.261
• InChiKey: KWICUYZLFNKYIA-DTWKUNHWSA-N

物化性质

• 沸点：
  280.1±20.0 °C(Predicted)
• 密度：
  1.138±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  38.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  tert-butyl (1S,4R)-2-oxa-3-aza-bicyclo-[2,2,2]oct-5-ene-3-carboxylate 在 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 4.25h， 以76%的产率得到3-aza-2-oxabicyclo[2.2.2]oct-5-ene trifluoroacetic acid salt
  参考文献：
  名称：

  [EN] ANTITHROMBOTIC ETHERS
  [FR] ETHERS ANTITHROMBOTIQUES

  摘要：

  这项申请涉及到公式I的化合物（或其前药或该化合物或前药的药用盐），以及其药物组合物，以及其作为Xa因子和/或凝血酶抑制剂的用途，以及其制备方法和中间体（I）。

  公开号：

  WO2004108677A1
• 作为产物：
  描述：

  1,3-环己二烯 在 5-O-Acetyl-2,3-O-isopropylidene-1-C-nitroso-D-ribofuranosyl 、 sodium carbonate 作用下， 以 甲醇 、 乙醇 为溶剂， 反应 27.0h， 生成 tert-butyl (1S,4R)-2-oxa-3-aza-bicyclo-[2,2,2]oct-5-ene-3-carboxylate
  参考文献：
  名称：

  Enantioselective Diels-Alder Reaction with an α-Chloronitrose Dienophile Derived from 5-O-Acetyl-2,3-isopropylidenedioxy-d-ribose

  摘要：

  晶体形式的5-O-乙酰基-2,3-异丙基二氧基-d-核糖内酯肟（8）通过从d-核糖合成，整体产率为40%。氯亚硝基二烯亲电试剂3b是通过t-BuOCl氧化8得到的，并与环状和非环状二烯10-13进行了不对称Diels-Alder反应，生成了晶体加合物14a-17a，产率良好且光学纯度极高（93-99%）。

  DOI：

  10.1055/s-2000-8214

文献信息

• Chiral Diels–Alder reaction between cyclopentadiene and nitroso derivatives: thermal isomerisation/racemisation of the adducts
  作者：Jean-Marc Heuchel、Sébastien Albrecht、Christiane Strehler、Albert Defoin、Céline Tarnus

  DOI：10.1016/j.tetasy.2012.09.005

  日期：2012.11

  Cyclopentadiene nitroso adducts 1a and ent-1a were synthesised in good yields and good enantiomeric excess from chiral chloro-nitroso derivatives 4 and 5 in the d-mannose and d-ribose series, respectively. The thermal racemisation of these adducts occurred below room temperature. Some other chiral Diels–Alder nitroso adducts were prepared in the d-mandelic, l-prolinol and d-O-methylprolinol series

  从d-甘露糖和d-核糖系列的手性氯亚硝基衍生物4和5分别以高收率和良好的对映异构体合成环戊二烯亚硝基加合物1a和ent - 1a。这些加合物的热消旋作用发生在室温以下。制备了其他一些手性Diels-Alder亚硝基加合物，分别为d-扁桃，l-脯氨醇和d- O-甲基脯氨醇，并根据N取代对它们进行了热异构化。从ent - 1a提出了手性酰胺基-环戊烯醇（+）- 2b（一种重要的生物有趣化合物的简单前体）的简单合成方法。
• New chiral amino acid-derived α-acyloxynitroso reagents for asymmetric nitroso Diels–Alder reactions
  作者：Hailing Li、Didier Gori、Cyrille Kouklovsky、Guillaume Vincent

  DOI：10.1016/j.tetasy.2010.05.016

  日期：2010.6

  The preparation of new chiral α-acyloxynitroso derivatives 4a–e as chiral dienophiles for the nitroso Diels–Alder reaction is reported. These compounds are obtained from amino acid-derived iodobenzene dicarboxylates and ketoximes, and are stable and easy-to-handle reagents. Initial studies for their nitroso Diels–Alder reactions with cyclohexadiene are also reported.

  据报道，制备了新的手性α-酰氧基亚硝基衍生物4a - e，作为亚硝基Diels-Alder反应的手性亲二烯体。这些化合物是从氨基酸衍生的碘代苯二羧酸盐和酮肟中获得的，是稳定且易于处理的试剂。还报道了它们与亚硝基Diels-Alder与环己二烯反应的初步研究。
• Vanadium-Catalyzed Oxidation of tert-Butyl N-Hydroxycarbamate to tert-Butyl Nitrosoformate and Its Diels–Alder Reaction with Simple and Functionalized Dienes
  作者：Yujiro Hoshino、Kenzo Suzuki、Kiyoshi Honda

  DOI：10.1055/s-0032-1317148

  日期：——

  A general and efficient vanadium-catalyzed oxidation of tert-butyl N-hydroxycarbamate to tert-butyl nitrosoformate using alkyl hydroperoxides as terminal oxidants has been developed. The intermediate nitroso compound was trapped by in situ Diels–Alder reaction with simple and functionalized dienes, providing general access to a variety of functionalized 3,6-dihydro-2H-1,2-oxazines.

  已经开发了使用烷基氢过氧化物作为末端氧化剂将 N-羟基氨基甲酸叔丁酯氧化成亚硝基甲酸叔丁酯的通用且有效的钒催化氧化。中间体亚硝基化合物通过与简单和官能化二烯的原位 Diels-Alder 反应被捕获，提供了对各种官能化 3,6-二氢-2H-1,2-恶嗪的通用途径。
• Hall, Adrian; Bailey, Patrick D.; Rees, David C., Journal of the Chemical Society. Perkin Transactions 1 (2001), 2000, # 3, p. 329 - 343
  作者：Hall, Adrian、Bailey, Patrick D.、Rees, David C.、Rosair, Georgina M.、Wightman, Richard H.

  DOI：——

  日期：——
• Accessing nitrosocarbonyl compounds with temporal and spatial control via the photoredox oxidation of N-substituted hydroxylamines
  作者：Charles P. Frazier、Leoni I. Palmer、Andrey V. Samoshin、Javier Read de Alaniz

  DOI：10.1016/j.tetlet.2015.01.024

  日期：2015.6

  Photoredox catalysis is employed to generate highly reactive acylnitroso species from hydroxamic acid derivatives. The conditions are shown to be comparable to a previously developed transition metal aerobic oxidation and are amenable to a range of transformations including Diels-Alder and ene reactions. This unique application of such an approach gives access to temporal and spatial control in nitroso chemistry. Published by Elsevier Ltd.