benzyl 4,4-diphenyl-2-vinylpyrrolidine-1-carboxylate | 906542-21-0

• 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: benzyl 4,4-diphenyl-2-vinylpyrrolidine-1-carboxylate
• 英文别名: Benzyl 2-ethenyl-4,4-diphenylpyrrolidine-1-carboxylate；benzyl 2-ethenyl-4,4-diphenylpyrrolidine-1-carboxylate
• CAS: 906542-21-0
• 化学式: C₂₆H₂₅NO₂
• 分子量: 383.49
• InChiKey: KKRPELOIKNHWHX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.8
• 重原子数：
  29
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.19
• 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：

  benzyl 4,4-diphenyl-2-vinylpyrrolidine-1-carboxylate 在 potassium permanganate 、 sodium periodate 、 potassium carbonate 作用下， 以 水 、 叔丁醇 为溶剂， 生成 (+/-)-benzyl 4,4-diphenylproline carbamate
  参考文献：
  名称：

  金（I）催化的N-烯丙基氨基甲酸酯的对映选择性加氢胺化。

  摘要：

  用[（S）-1] Au2Cl2 [（S）-1 =（S）-3,5-t-Bu-4-MeO）1：2催化混合物处理N-4,5-己二烯基氨基甲酸酯2a [-MeOBIPHEP]和AgClO4在-40°C的间二甲苯中放置24小时，从而以97％的收率分离出2-乙烯基吡咯烷3a，ee值为81％。金（I）催化的对映选择性氢化胺化对于许多氨基甲酸酯基团和可承受的烯基部分的末端去位取代作用是有效的。

  DOI：

  10.1021/ol071108n
• 作为产物：
  描述：

  二苯乙腈 在 氯[2-(二叔丁基磷)二苯基]金 、 silver trifluoromethanesulfonate lithium aluminium tetrahydride 、 碳酸氢钠 、 二异丙胺 、 copper(I) bromide 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 乙醚 、 乙醇 、 水 为溶剂， 反应 4.0h， 生成 benzyl 4,4-diphenyl-2-vinylpyrrolidine-1-carboxylate
  参考文献：
  名称：

  用于与碳、氮和氧亲核试剂对艾伦烯进行分子内外加氢官能化的高活性 Au(I) 催化剂

  摘要：

  (2,2-二苯基-4,5-己二烯基)氨基甲酸苄酯 (4) 与 Au[P(t-Bu)2(o-biphenyl)]Cl (2) 和 AgOTf 的 1:1 催化混合物反应5 mol%) 在二恶烷中在 25 摄氏度下 45 分钟导致 4,4-二苯基-2-乙烯基吡咯烷-1-羧酸苄酯 (5) 的分离，产率为 95%。Au(I) 催化的 N-烯丙氨基甲酸酯的分子内加氢胺化耐受烷基和烯基碳原子处的取代，并且对于哌啶衍生物的形成是有效的。γ-羟基和δ-羟基丙二烯也在室温下几分钟内经历了金催化的分子内加氢烷氧基化，以高产率和高外选择性形成相应的氧杂环。2-烯基吲哚在室温下几分钟内经历金催化的分子内加氢芳基化，以良好的产率形成4-乙烯基四氢咔唑。

  DOI：

  10.1021/ja062045r

文献信息

• Synthesis of chiral mono(N-heterocyclic carbene) palladium and gold complexes with a 1,1'-biphenyl scaffold and their applications in catalysis
  作者：Lian-jun Liu、Feijun Wang、Wenfeng Wang、Mei-xin Zhao、Min Shi

  DOI：10.3762/bjoc.7.64

  日期：——

  Axially chiral mono(NHC)–Pd(II) and mono(NHC)–Au(I) complexes with one side shaped 1,1'-biphenyl backbone have been prepared from chiral 6,6'-dimethoxybiphenyl-2,2'-diamine. The complexes were characterized by X-ray crystal structure diffraction. The Pd(II) complex showed good catalytic activities in the Suzuki–Miyaura and Heck–Mizoroki coupling reactions, and the (S)-Au(I) complexes also showed good catalytic activities in the asymmetric intramolecular hydroamination reaction to give the corresponding product in moderate ee.

  具有轴向手性的单(NHC)-Pd(II)和单(NHC)-Au(I)配合物，具有一侧成形的1,1'-联苯骨架，已经从手性6,6'-二甲氧基联苯-2,2'-二胺制备而成。这些配合物通过X射线晶体结构衍射进行了表征。Pd(II)配合物在Suzuki-Miyaura和Heck-Mizoroki偶联反应中表现出良好的催化活性，而(S)-Au(I)配合物在不对称分子内氢胺化反应中也表现出良好的催化活性，以适度的ee产生相应的产物。
• Synthesis of a Mechanically Planar Chiral Rotaxane Ligand for Enantioselective Catalysis
  作者：Andrew W. Heard、Stephen M. Goldup

  DOI：10.1016/j.chempr.2020.02.006

  日期：2020.4

  been explored in catalysis and sensing. However, so far, the applications of one of the most intriguing properties of interlocked molecules, their ability to display stereogenic units that do not rely on the stereochemistry of their covalent subunits, termed “mechanical chirality,” have yet to be properly explored, and prototypical demonstration of the applications of mechanically chiral rotaxanes remain

  轮烷是互锁分子，其中分子环被困在哑铃形轴上，因为它无法从庞大的端基上逸出，从而形成所谓的机械键。互锁分子主要作为分子机器的组成部分进行研究，但在催化和传感方面也探索了通过将一个分子穿过另一个分子所产生的拥挤、灵活的环境。然而，到目前为止，互锁分子最有趣的特性之一的应用，它们展示立体单元的能力，不依赖于其共价亚基的立体化学，称为“机械手性”，尚未得到适当的探索，并且机械手性轮烷应用的原型演示仍然很少。这里，
• Stable yet reactive cationic gold catalysts with carbon based counterions
  作者：Xiaojun Zeng、Shiwen Liu、Bo Xu

  DOI：10.1039/c6ra19064b

  日期：——

  Widely applicable cationic gold catalysts with a carbon based counterion.

  具有碳基对离子的广泛适用的阳离子金催化剂。
• Gold(I)-Catalyzed Intramolecular Amination of Allylic Alcohols With Alkylamines
  作者：Paramita Mukherjee、Ross A. Widenhoefer

  DOI：10.1021/ol103175w

  日期：2011.3.18

  A 1:1 mixture of (1)AuCl [1 = P(t-Bu)2o-biphenyl] and AgSbF6 catalyzes the intramolecular amination of allylic alcohols with alkylamines to form substituted pyrrolidine and piperidine derivatives. Gold(I)-catalyzed cyclization of (R,Z)-8-(N-benzylamino)-3-octen-2-ol (96% ee, 95% de) led to isolation of (R,E)-1-benzyl-2-(1-propenyl)piperidine in 99% yield with 96% ee, consistent with the net syn addition

  ( 1 )AuCl [ 1 = P( t- Bu) 2 o-联苯]和AgSbF 6的1:1混合物催化烯丙醇与烷基胺的分子内胺化，形成取代的吡咯烷和哌啶衍生物。金 (I) 催化 ( R,Z )-8-( N -苄氨基)-3-辛烯-2-醇 (96% ee, 95% de) 环化导致分离 ( R,E )-1-苄基-2-(1-丙烯基)哌啶的产率为 99%，ee 率为 96%，这与胺相对于离开的羟基的净顺式加成一致。
• Exploring the Scope of Nitrogen Acyclic Carbenes (NACs) in Gold-Catalyzed Reactions
  作者：Camino Bartolomé、Domingo García-Cuadrado、Zoraida Ramiro、Pablo Espinet

  DOI：10.1021/om100507r

  日期：2010.8.23

  The catalytic activity of the recently reported nitrogen acyclic carbene (NAG) complexes of gold(I) has been investigated and compared with the reported activity of other gold(I) and gold(III) complexes. The complexes studied, [AuClC(NEt2)(NHTol-p)}], [AuClC(NEt2)(NHXylyl)}], and [Au(NTf2)C(NEt2)(NHXylyl)}], are very active in processes such as the rearrangement of homo-propargylsulfoxides, the intramolecular hydroamination of N-allenyl carbamates, the intramolecular hydroalkoxylation of allenes, the hydroarylation of acetylenecarboxylic acid ester, and the benzylation of anisole. Although the NAG ligands have not been optimized for the reactions tested, the yields obtained are usually similar and sometimes better than those reported with other catalysts, showing that the presence of N-H bonds and the wider N-C-N angle in the NAG (as compared to the NHC) complexes are not detrimental for the catalysis. For the hydroarylation reaction (where two competing products can be formed), the NAG complexes allow favoring one over the other. For the benzylation of anisole the selectivity is complementary to that obtained using H[AuCl4] as catalyst, and depending on the substrate, the NAG gold(III) complexes outperform the activity of H[AuCl4]. On average, the reactivity found suggests that the basicity of NACs toward gold(I) is very similar to that of NHCs and higher than that of phosphines.