N-Allyl-N-tert-butylcarbonyl-N-cinnamylamine | 219668-51-6

• 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: N-Allyl-N-tert-butylcarbonyl-N-cinnamylamine
• 英文别名: tert-butyl N-allyl-N-cinnamylcarbamate；N-Boc-N-allyl-trans-cinnamylamine；tert-butyl N-[(E)-3-phenylprop-2-enyl]-N-prop-2-enylcarbamate
• CAS: 219668-51-6
• 化学式: C₁₇H₂₃NO₂
• 分子量: 273.375
• InChiKey: UPPWUIQBGVXPGN-FMIVXFBMSA-N

物化性质

• 沸点：
  379.4±32.0 °C(Predicted)
• 密度：
  1.018±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  20
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-Allyl-N-tert-butylcarbonyl-N-cinnamylamine 在 <(c-C6H11)2(c-Me2NClC5H9)P>2Cl2Ru=CHPh 作用下， 以 甲醇 为溶剂， 反应 30.0h， 生成 N-Boc-3-吡咯啉
  参考文献：
  名称：

  Ring-Closing Metathesis in Methanol and Water

  摘要：

  The ring-closing metathesis (RCM) of acyclic dienes in both methanol and water has been achieved through the use of water-soluble ruthenium alkylidenes. These alkylidenes react readily with acyclic olefins in protic solvents, but they do not cyclize alpha,omega-dienes because of the instability of the resulting methylidene. Successful cyclization has been achieved through simple substrate modification-incorporation of an olefin substituent allows cyclization to proceed in good yield. A methyl-substituted substrate was cyclized in 60% conversion in methanol, and the incorporation of a phenyl substituent resulted in nearly quantitative cyclization. Phenyl-substituted substrates are best suited for the reaction, as a more stable, active catalyst is regenerated upon each catalyst turnover. Using this methodology, 90% conversion of a water-soluble substrate to a substituted cyclopentene has been achieved in aqueous solution. This methodology has also been successfully applied to increase RCM yields in organic solvents.

  DOI：

  10.1021/jo981678o
• 作为产物：
  描述：

  叔丁氧基 N-氨基甲酸丙烯 、 Cinnamyl bromide 在 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 16.0h， 以80%的产率得到N-Allyl-N-tert-butylcarbonyl-N-cinnamylamine
  参考文献：
  名称：

  Ring-Closing Metathesis in Methanol and Water

  摘要：

  The ring-closing metathesis (RCM) of acyclic dienes in both methanol and water has been achieved through the use of water-soluble ruthenium alkylidenes. These alkylidenes react readily with acyclic olefins in protic solvents, but they do not cyclize alpha,omega-dienes because of the instability of the resulting methylidene. Successful cyclization has been achieved through simple substrate modification-incorporation of an olefin substituent allows cyclization to proceed in good yield. A methyl-substituted substrate was cyclized in 60% conversion in methanol, and the incorporation of a phenyl substituent resulted in nearly quantitative cyclization. Phenyl-substituted substrates are best suited for the reaction, as a more stable, active catalyst is regenerated upon each catalyst turnover. Using this methodology, 90% conversion of a water-soluble substrate to a substituted cyclopentene has been achieved in aqueous solution. This methodology has also been successfully applied to increase RCM yields in organic solvents.

  DOI：

  10.1021/jo981678o

文献信息

• Flavin-Mediated Visible-Light [2+2] Photocycloaddition of Nitrogen- and Sulfur-Containing Dienes
  作者：Michael Jirásek、Karolína Straková、Tomáš Neveselý、Eva Svobodová、Zdeňka Rottnerová、Radek Cibulka

  DOI：10.1002/ejoc.201601377

  日期：2017.4.18

  [2+2] Photocycloaddition mediated by 1-butyl-3-methyl-7,8-dimethoxyalloxazine (1) is shown as an effective tool to cyclise ω-phenyl and ω,ω'-diphenyl-4-aza-1,6-heptadienes, with the nitrogen atom protected by acylation or quaternisation, used towards the synthesis of variety of phenyl- and diphenyl-3-azabicyclo[3.2.0]heptanes and their corresponding quaternary salts. Thia-derivatives with the sulfur

  [2+2] 1-丁基-3-甲基-7,8-二甲氧基恶嗪 (1) 介导的光环加成反应是环化 ω-苯基和 ω,ω'-diphenyl-4-aza-1,6 的有效工具-庚二烯，其氮原子被酰化或季铵化保护，用于合成各种苯基-和二苯基-3-氮杂双环[3.2.0]庚烷及其相应的季盐。硫原子以砜基团形式存在的硫杂衍生物经历类似的环化。有利地，与先前描述的通过UV光照射提供氮杂双环[3.2.0]庚烷的程序相比，可见光(400nm)用于使用1的环加成。通过合成双环季铵盐 6-苯基氮杂双环 [3.2. 0]已知具有生物活性的庚烷或手性螺铵盐。还发现黄素 1 可提供富电子肉桂基衍生物的高效 E→Z 异构化，以产生富含 Z-异构体的混合物（Z:E 比率高达 77:23）。
• The Stereoselective Synthesis of 2-Substituted 3-Azabicyclo[3.2.0]heptanes by Intramolecular [2+2]-Photocycloaddition Reactions
  作者：Thorsten Bach、Christa Krüger、Klaus Harms

  DOI：10.1055/s-2000-6261

  日期：——

  The stereoselective synthesis of the 3-azabicyclo[3.2.0]heptanes 6, 12, 13, 17, 22, 23 and 24 by an intramolecular [2+2]-photocycloaddition is described. The product yield was good to excellent in almost all cases studied (65-87%) except for a single example (21 → 24) in which a low yield was recorded (22%). The facial diastereoselectivity of the reaction is high if α-branched N,N-diallylamines are employed as starting materials which either bear a comparably bulky α-substituent (25) or the α-substituent of which is connected to the nitrogen atom via an oxazolidinone ring (16, 19, 20, 21). These diallylamines were readily prepared from methionine and it was shown that their preparation proceeded free of racemization. The photocycloaddition could be conducted in two ways. The more general method is based on the Cu-catalyzed reaction which was carried out with Cu(OTf)2 in diethyl ether and is applicable to essentially all substrates under scrutiny. The N-cinnamyl substituted substrates 5, 11, 16 and 25 which possess a comparably low lying T1 state reacted well in a triplet-sensitized process employing acetophenone as the sensitizer and acetone as the solvent.

  本文描述了通过分子内[2+2]光环加成反应合成3-氮杂双环[3.2.0]庚烷6、12、13、17、22、23和24的手性选择性合成方法。在所有研究的情况中，产物收率良好至优异（65-87%），仅有一个例外（21→24）记录到较低的收率（22%）。如果使用α-支链的N,N-二烯丙基胺作为起始材料，这些材料要么带有相对较大的α-取代基（25），要么其α-取代基通过恶唑烷酮环与氮原子相连（16、19、20、21），反应的面选择性非常高。这些二烯丙基胺很容易从甲硫氨酸制备，并且证明其制备过程没有发生消旋化。光环加成反应可以通过两种方式进行。更通用的方法是基于铜催化的反应，使用Cu(OTf)2在二乙醚中进行，适用于几乎所有待研究的底物。拥有相对较低T1态的N-肉桂基取代底物5、11、16和25在三重态敏化过程中反应良好，使用乙酰苯作为敏化剂，丙酮作为溶剂。
• Ring-Closing Metathesis in Methanol and Water
  作者：Thomas A. Kirkland、David M. Lynn、Robert H. Grubbs

  DOI：10.1021/jo981678o

  日期：1998.12.1

  The ring-closing metathesis (RCM) of acyclic dienes in both methanol and water has been achieved through the use of water-soluble ruthenium alkylidenes. These alkylidenes react readily with acyclic olefins in protic solvents, but they do not cyclize alpha,omega-dienes because of the instability of the resulting methylidene. Successful cyclization has been achieved through simple substrate modification-incorporation of an olefin substituent allows cyclization to proceed in good yield. A methyl-substituted substrate was cyclized in 60% conversion in methanol, and the incorporation of a phenyl substituent resulted in nearly quantitative cyclization. Phenyl-substituted substrates are best suited for the reaction, as a more stable, active catalyst is regenerated upon each catalyst turnover. Using this methodology, 90% conversion of a water-soluble substrate to a substituted cyclopentene has been achieved in aqueous solution. This methodology has also been successfully applied to increase RCM yields in organic solvents.