crotonaldehyde N-benzylimine | 63459-08-5

• 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: crotonaldehyde N-benzylimine
• 英文别名: (1E)-N-Benzylbut-2-en-1-imine；N-benzylbut-2-en-1-imine
• CAS: 63459-08-5
• 化学式: C₁₁H₁₃N
• 分子量: 159.231
• InChiKey: WKKLWSDBTLROPG-UHFFFAOYSA-N

物化性质

• 沸点：
  110-120 °C(Press: 0.02 Torr)
• 密度：
  0.86±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  12.4
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  crotonaldehyde N-benzylimine 在 sodium hexamethyldisilazane 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 4.42h， 生成 rac-(4aR,7aR,11(1)S)-methyl 7-benzyl-6-oxo-1,2,3,4,4a,6,7,7a,10,11-decahydrodibenzo[d,e][1,3]oxazine-4-carboxylate
  参考文献：
  名称：

  The enantioselective synthesis of tetracyclic methyllycaconitine analogues

  摘要：

  A new enantioselective synthesis of ABEF ring analogues of methyllycaconitine has been developed using a chiral cobalt(III) salen-catalyzed Diels-Alder reaction to form the B ring. Subsequent elaboration to form the A, E and F rings was achieved by sequential Dieckmann, Mannich and Wacker-type cyclizations to afford tetracyclic analogues in 97.5% ee. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2011.08.026
• 作为产物：
  描述：

  巴豆醛 、 苄胺 在 4 A molecular sieve 作用下， 以 二氯甲烷 为溶剂， 生成 crotonaldehyde N-benzylimine
  参考文献：
  名称：

  Synthesis of .beta.,.gamma.-unsaturated amino acids by the Strecker reaction

  摘要：

  DOI：

  10.1021/jo00188a026

文献信息

• Novel transformation of α,β-unsaturated aldehydes and ketones into γ-amino alcohols or 1,3-oxazines via a 4 or 5 step, one-pot sequence
  作者：Adam D. J. Calow、Andrei S. Batsanov、Elena Fernández、Cristina Solé、Andrew Whiting

  DOI：10.1039/c2cc36129a

  日期：——

  An efficient, 4-step, one-pot, highly stereoselective route to γ-amino alcohols has been developed via an in situ α,β-unsaturated imine formation, β-boration, reduction (CN) and oxidation (C–B) sequence and especially for certain water-soluble γ-amino alcohols, a further step can be added to directly access the corresponding 1,3-oxazine derivatives.

  开发了一种高效的四步一锅法高度立体选择性合成γ-氨基醇的路线，通过原位形成α，β-不饱和亚胺、β-硼化、还原（CN）和氧化（C-B）的顺序，特别是对于某些水溶性γ-氨基醇，还可以增加一步直接获得相应的1,3-噁嗪衍生物。
• Highly Diastereoselective Synthesis of Tetrahydropyridines by a C–H Activation–Cyclization–Reduction Cascade
  作者：Simon Duttwyler、Colin Lu、Arnold L. Rheingold、Robert G. Bergman、Jonathan A. Ellman

  DOI：10.1021/ja2119833

  日期：2012.3.7

  A versatile reaction cascade leading to highly substituted 1,2,3,6-tetrahydropyridines has been developed. It comprises rhodium(I)-catalyzed C-H activation-alkyne coupling followed by electrocyclization and subsequent acid/borohydride-promoted reduction. This one-pot procedure affords the target compounds in up to 95% yield with >95% diastereomeric purity.

  已开发出一种可产生高度取代的 1,2,3,6-四氢吡啶的通用反应级联。它包括铑 (I) 催化的 CH 活化-炔烃偶联，然后是电环化和随后的酸/硼氢化物促进的还原。这一一锅法可提供高达 95% 的收率和 >95% 非对映体纯度的目标化合物。
• A Simple and Inexpensive Method for the Preparation of Imines and Azadienes
  作者：A. Saoudi、A. Benguedach、H. Benhaoua

  DOI：10.1080/00397919508015438

  日期：1995.8

  Abstract A number of imines and azadienes were prepared in high yield and good purity by using the condensation reactions of various aldehydes and ketones with amines over natural Algerian bentonite.

  摘要 利用各种醛、酮与胺在天然阿尔及利亚膨润土上的缩合反应，以高收率和良好的纯度制备了多种亚胺和氮杂二烯。
• Understanding α,β-Unsaturated Imine Formation from Amine Additions to α,β-Unsaturated Aldehydes and Ketones: An Analytical and Theoretical Investigation
  作者：Adam D. J. Calow、Jorge J. Carbó、Jessica Cid、Elena Fernández、Andrew Whiting

  DOI：10.1021/jo5007366

  日期：2014.6.6

  and DFT calculations have been used to understand what factors govern the selectivity in the addition of primary amines to α,β-unsaturated aldehydes and ketones, i.e., 1,2- versus 1,4-addition. It has been found that the 1,2-addition products (α,β-unsaturated imines following addition and elimination) usually predominate for most systems. However, exceptions, such as methyl vinyl ketone, selectively give

  结合使用原位红外光谱（ReactIR）和DFT计算来了解哪些因素决定了将伯胺添加到α，β-不饱和醛和酮中的选择性，即1,2-对1,4-添加。已经发现，在大多数系统中，1,2-加成产物（加成和消除后的α，β-不饱和亚胺）通常占主导地位。但是，诸如甲基乙烯基酮之类的例外情况会选择性地产生1,4-加成产物。这已通过DFT计算得到了合理化，该计算表明涉及主要构象效应，主要受羰基取代基的空间效应控制，从而形成了一种模型，该模型提供了简单，可预测的α，β-不饱和亚胺制备方法，可用于原位合成。
• 1-Azadiene complexes of zirconocene
  作者：Jeremy M. Davis、Richard J. Whitby、Albert Jaxa-Chamiec

  DOI：10.1039/c39910001743

  日期：——

  1-Azadiene complexes of zirconocene were prepared by ligand exchange between zirconocene butene and the 1-azadiene, and by a C–H activation route from allylic amines; they are best described as 1-zircona-2-azacyclopent-3-enes and 5-unsubstituted examples are fluxional.

  1-氮烯复合物是通过锆茂丁烯与1-氮烯之间的配体交换，以及通过从烯丙胺进行C–H活化反应制备的；它们最恰当地被描述为1-锆烯-2-氮环戊-3-烯，且5个未取代的例子是流动的。