Benzhydryl-[(E)-but-2-en-(E)-ylidene]-amine | 124739-77-1

• 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: Benzhydryl-[(E)-but-2-en-(E)-ylidene]-amine
• 英文别名: N-benzhydrylbut-2-en-1-imine
• CAS: 124739-77-1
• 化学式: C₁₇H₁₇N
• 分子量: 235.329
• InChiKey: KOAHVZHHTXMYNY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.42
• 重原子数：
  18.0
• 可旋转键数：
  4.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  12.36
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  Benzhydryl-[(E)-but-2-en-(E)-ylidene]-amine 在 吡啶 、 三苯基膦 、 联硼酸频那醇酯 、 copper(l) chloride 、 sodium t-butanolate 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 4.0h， 生成 4-[N-(diphenylmethyl)acetamido]butan-2-yl acetate
  参考文献：
  名称：

  A Selective Transformation of Enals into Chiral γ-Amino Alcohols

  摘要：

  A one-pot synthesis of chiral amino alcohols from alpha,beta-unsaturated aldehydes is reported which circumvents competitive 1,2-versus 1,4-boryl addition, by means of using a sterically hindered amine-derived imine. In addition to the complete chemoselectivity, modification of the Cu(I) catalyst with readily available chiral diphosphines, such as (R)-DM-BINAP, gave the 1,4-boryl addition products with high levels of asymmetric induction.

  DOI：

  10.1021/ol4022029
• 作为产物：
  描述：

  1-benzhydryl-2-vinylaziridine 在 bis(1,5-cyclooctadiene)nickel (0) 、 1,3-bis(2,5-diisopropylphenyl)-4,5-dihydroimidazolin-2-ylidene 作用下， 以 甲苯 为溶剂， 生成 Benzhydryl-[(E)-but-2-en-(E)-ylidene]-amine
  参考文献：
  名称：

  Nickel-catalyzed reactions of vinyl aziridines and aziridinylen-ynes

  摘要：

  Ni/NHC was found to catalyze the rearrangement of vinyl aziridines and aziridinylen-ynes under mild conditions. Published by Elsevier Ltd.

  DOI：

  10.1016/j.tetlet.2008.09.056

文献信息

• Chiral Counteranions in Asymmetric Transition-Metal Catalysis:  Highly Enantioselective Pd/Brønsted Acid-Catalyzed Direct α-Allylation of Aldehydes
  作者：Santanu Mukherjee、Benjamin List

  DOI：10.1021/ja074678r

  日期：2007.9.1

  Pd/chiral acid-catalyzed α-allylation of α-branched aldehydes with an allyl amine as the allylating species that creates all-carbon quaternary stereogenic centers in high yields and enantioselectivities. To our knowledge, this is the first time that a chiral anionic ligand is applied for achieving asymmetric induction in a palladium-catalyzed allylic alkylation reaction.

  我们开发了一种高度对映选择性 Pd/手性酸催化的 α-支化醛与烯丙胺作为烯丙基化物质的 α-烯丙基化反应，以高产率和对映选择性创建全碳季立体中心。据我们所知，这是首次应用手性阴离子配体在钯催化的烯丙基烷基化反应中实现不对称诱导。
• Conjugated imines and iminium salts as versatile acceptors of nucleophiles
  作者：Makoto Shimizu、Iwao Hachiya、Isao Mizota

  DOI：10.1039/b814930e

  日期：——

  development of synthetic methodologies where nucleophilic addition reactions to imino carbons are utilized in crucial steps. This article summarizes double nucleophilic addition reactions with alpha,beta-unsaturated aldimines, addition reactions using alkynyl imines, "umpoled" reactions of alpha-imino esters, and the use of iminium salts as reactive electrophiles.

  对涉及生物活性和功能材料的含氮分子的兴趣日益增长，刺激了合成方法的最新发展，在关键步骤中利用了对亚氨基碳的亲核加成反应。本文总结了与α，β-不饱和醛亚胺的双亲核加成反应，使用炔基亚胺的加成反应，α-亚氨基酯的“团聚”反应以及亚胺盐作为反应性亲电试剂的使用。
• One-pot catalytic asymmetric borylation of unsaturated aldehyde-derived imines; functionalisation to homoallylic boronate carboxylate ester derivatives
  作者：Alba Pujol、Adam D. J. Calow、Andrei S. Batsanov、Andrew Whiting

  DOI：10.1039/c4ob02657h

  日期：——

  β-boryl aldehydes. The instability of the β-boryl aldehydes meant that derivatisation was required and routes to both acetal derivatives and homoallylic boronates were examined. β-Boryl acetals were also found to be unstable, however, the formation of homoallylic boronate derivatives using an in situ imine hydrolysis-Wittig olefination protocol was found to be suitable, resulting in an efficient synthesis

  使用一锅法研究了原位形成的α，β-不饱和醛衍生的亚胺的β-硼化反应，作为通往β-硼醛的途径。β-硼醛的不稳定性意味着需要进行衍生化，并研究了同时生成乙缩醛衍生物和均烯丙基硼酸酯的途径。还发现β-甲酰基乙缩醛是不稳定的，但是，发现使用原位亚胺水解-Wittig烯烃化方案形成均烯丙基硼酸酯衍生物是合适的，从而导致具有高对映体过量的有效合成。
• Oxazoline-Based Organocatalyst for Enantioselective Strecker Reactions: A Protocol for the Synthesis of Levamisole
  作者：Arghya Sadhukhan、Debashis Sahu、Bishwajit Ganguly、Noor-ul H. Khan、Rukhsana I. Kureshy、Sayed H. R. Abdi、E. Suresh、Hari C. Bajaj

  DOI：10.1002/chem.201302007

  日期：2013.10.11

  catalyze asymmetric Strecker reactions of various aromatic and aliphatic N‐benzhydrylimines with trimethylsilyl cyanide (TMSCN) as a cyanide source at −20 °C to give α‐aminonitriles in high yield (96 %) with excellent chiral induction (up to 98 % ee). DFT calculations have been performed to rationalize the enantioselective formation of the product with the organocatalyst in these reactions. The organocatalyst

  已发现基于手性恶唑啉的有机催化剂可在-20°C下有效催化各种芳族和脂族N-苯甲酰肼与三甲基甲硅烷基氰化物（TMSCN）作为氰化物源的不对称Strecker反应，从而以高收率（96％）产生α-氨基腈具有出色的手性诱导作用（高达98％  ee）。在这些反应中，已经进行了DFT计算以使产物与有机催化剂的对映选择性形成合理化。有机催化剂已通过单晶X射线衍射分析以及其他分析方法进行了表征。该方案已扩展到以高收率和高对映选择性合成药学上重要的药物分子左旋咪唑。
• Double Diastereoselective Approach to Chiral <i>syn</i>- and <i>anti</i>-1,3-Diol Analogues through Consecutive Catalytic Asymmetric Borylations
  作者：Alba Pujol、Andrew Whiting

  DOI：10.1021/acs.joc.7b00854

  日期：2017.7.21

  Homoallylic boronate carboxylate esters derived from unsaturated aldehydes via an imination, β-borylation, imine hydrolysis, and Wittig trapping sequence, were subjected to a second boryl addition to give 1,3-diborylated carboxylate esters. Control of the absolute and relative stereochemistry of the two new 1,3-stereogenic centers was achieved through: (1) direct chiral catalyst controlled asymmetric borylation

  经由亚胺基化，β-硼化，亚胺水解和Wittig捕获序列衍生自不饱和醛的均烯丙基硼酸酯羧酸酯，进行第二次硼烷基加成，得到1,3-二硼酸酯化的羧酸酯。通过以下方法控制两个新的1,3-立体异构中心的绝对和相对立体化学：（1）直接手性催化剂控制高ee在不饱和亚胺上的第一个立体中心的不对称硼化；（2）使用手性催化剂的不饱和酯的双非对映选择性控制的硼酸酯化，大大克服了来自第一个手性硼烷基中心的导向作用，从而使差的（不匹配的）到良好的（匹配的）非对映控制。随后，