N-(1-phenylallyl)-N-phenylbenzamide | 147428-19-1

• 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: N-(1-phenylallyl)-N-phenylbenzamide
• 英文别名: N-phenyl-N-(1-phenylprop-2-enyl)benzamide
• CAS: 147428-19-1
• 化学式: C₂₂H₁₉NO
• 分子量: 313.399
• InChiKey: RGKILWRMHBEDFB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  24
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N-(1-phenylallyl)-N-phenylbenzamide 在 偶氮二异丁腈 、 三苯基氢化锡 、 水 作用下， 以 苯 为溶剂， 反应 26.5h， 生成 2-(benzoyloxy)-1-phenyl-1-(phenylamino)propane
  参考文献：
  名称：

  Functional group manipulation via organoselenium- and halogen-induced cyclofunctionalization/hydrolysis of allylic benzimidates, tertiary benzamides, and benzamidines. Regioflexible synthesis of amino alcohol derivatives

  摘要：

  Allylic benzimidates were treated with benzeneselenenyl halides in chloroform or acetonitrile to give, via 5-exo cyclofunctionalization/hydrolysis, 3-(benzoyloxy)-2-(phenylamino)-1-(phenylselenenyl)-alkanes in fair yields. Allylic tertiary benzamides afforded 2-(benzoyloxy)-3-(phenylamino)-1-(phenylselenenyl)alkanes when submitted to similar reaction conditions. Bromoalkanes, functionalized in an analogous way, were obtained after hydrolytic workup when bromine was added to allylic benzimidates and tertiary benzamides. In some of these reactions, products of 6-endo cyclofunctionalization/hydrolysis (1-(benzoyloxy)-3-(phenylamino)-2-bromoalkanes) were also formed. The addition of benzeneselenenyl bromide to some a-substituted allylic benzimidates and tertiary benzamides was diastereoselective (0 < de < 90%, depending on conditions) with a preference for threo isomer formation. Hydrodeselenation/hydrodebromination of the cyclofunctionalization/hydrolysis products was efficiently effected (88-100% yield) by treatment of the products with triphenyltin hydride in refluxing benzene containing a catalytic amount of azobis(isobutyronitrile). The proper choice of allylic benzimidate/tertiary benzamide allowed the preparation of amino alcohol derivatives in which the 1,2-orientation of the functional groups, relative to the carbon backbone, could be varied in a controlled and predictable manner. The regioflexibility of the process was demonstrated for primary, secondary, and tertiary positions. When allylic benzamidines were submitted to the cyclofunctionalization/hydrolysis reaction conditions using benzeneselenenyl bromide as the electrophilic reagent, 5-phenylselenenyl(methyl) -substituted dihydroimidazoles were obtained.

  DOI：

  10.1021/jo00061a009
• 作为产物：
  描述：

  N-苯基亚胺苄基氯 在 双(乙腈)氯化钯(II) 、 sodium hydride 作用下， 以 四氢呋喃 、 二氯甲烷 、 mineral oil 为溶剂， 反应 4.0h， 生成 N-(1-phenylallyl)-N-phenylbenzamide
  参考文献：
  名称：

  钯催化烯丙酰胺的反马尔科夫尼科夫氧化为受保护的 β-氨基醛

  摘要：

  描述了从烯丙胺或线性烯丙醇制备 N-保护的 β-氨基醛的一般方法。在这里，在环境条件下，在 tBuOH 中实现了 Pd(II) 催化的 N-保护烯丙基胺与苯醌的氧化，对抗马尔科夫尼科夫醛产物具有出色的选择性，并且完全保留了烯丙基碳上的构型。该方法显示出广泛的底物范围，并且可以耐受一系列保护基团。此外，β-氨基醛可以通过钯催化的自串联反应直接从受保护的烯丙醇中获得，并描述了该方法在β-肽醛合成中的应用。从机理上看，我们证明 tBuOH 在反应中充当亲核试剂，并且最初形成的叔丁基醚经历异丁烯的自发损失以产生醛产物。此外，tBuOH 可以按化学计量使用，从而拓宽反应的溶剂范围。伯醇和仲醇不会发生消除，从而可以分离出缩醛，随后可以将其水解为相应的醛产物。

  DOI：

  10.1021/ja510163w

文献信息

• Increased Efficiency in Cross-Metathesis Reactions of Sterically Hindered Olefins
  作者：Ian C. Stewart、Christopher J. Douglas、Robert H. Grubbs

  DOI：10.1021/ol702624n

  日期：2008.2.1

  Efficiency in olefin cross-metathesis reactions is affected upon reducing the steric bulk of N-heterocyclic carbene ligands of ruthenium-based catalysts. For the formation of disubstituted olefins containing one or more allylic substituents, the catalyst bearing N-tolyl groups is more efficient than the corresponding N-mesityl catalyst. In contrast, the formation of trisubstituted olefins is more efficient

  减少钌基催化剂的N-杂环卡宾配体的空间体积会影响烯烃的交叉复分解反应的效率。为了形成含有一个或多个烯丙基取代基的二取代烯烃，带有N-甲苯基的催化剂比相应的N-间苯二甲酰基催化剂更有效。相反，使用含N-间苯三甲的催化剂形成三取代的烯烃更有效。描述了一个解释这种二分法的假设。
• Oxazoline-Mediated Interannular Cyclopalladation of Ferrocene: Chiral Palladium(<scp>II</scp>) Catalysts for the Enantioselective Aza-Claisen Rearrangement
  作者：Albert Moyano、Malgorzata Rosol、Rosa M. Moreno、Concepción López、Miguel A. Maestro

  DOI：10.1002/anie.200462434

  日期：2005.3.11
• Palladium-Catalyzed Anti-Markovnikov Oxidation of Allylic Amides to Protected β-Amino Aldehydes
  作者：Jia Jia Dong、Emma C. Harvey、Martín Fañanás-Mastral、Wesley R. Browne、Ben L. Feringa

  DOI：10.1021/ja510163w

  日期：2014.12.10

  directly from protected allylic alcohols via palladium-catalyzed autotandem reactions, and the application of this method to the synthesis of β-peptide aldehydes is described. From a mechanistic perspective, we demonstrate that tBuOH acts as a nucleophile in the reaction and that the initially formed tert-butyl ether undergoes spontaneous loss of isobutene to yield the aldehyde product. Furthermore, tBuOH

  描述了从烯丙胺或线性烯丙醇制备 N-保护的 β-氨基醛的一般方法。在这里，在环境条件下，在 tBuOH 中实现了 Pd(II) 催化的 N-保护烯丙基胺与苯醌的氧化，对抗马尔科夫尼科夫醛产物具有出色的选择性，并且完全保留了烯丙基碳上的构型。该方法显示出广泛的底物范围，并且可以耐受一系列保护基团。此外，β-氨基醛可以通过钯催化的自串联反应直接从受保护的烯丙醇中获得，并描述了该方法在β-肽醛合成中的应用。从机理上看，我们证明 tBuOH 在反应中充当亲核试剂，并且最初形成的叔丁基醚经历异丁烯的自发损失以产生醛产物。此外，tBuOH 可以按化学计量使用，从而拓宽反应的溶剂范围。伯醇和仲醇不会发生消除，从而可以分离出缩醛，随后可以将其水解为相应的醛产物。
• Functional group manipulation via organoselenium- and halogen-induced cyclofunctionalization/hydrolysis of allylic benzimidates, tertiary benzamides, and benzamidines. Regioflexible synthesis of amino alcohol derivatives
  作者：Lars Engman

  DOI：10.1021/jo00061a009

  日期：1993.4

  Allylic benzimidates were treated with benzeneselenenyl halides in chloroform or acetonitrile to give, via 5-exo cyclofunctionalization/hydrolysis, 3-(benzoyloxy)-2-(phenylamino)-1-(phenylselenenyl)-alkanes in fair yields. Allylic tertiary benzamides afforded 2-(benzoyloxy)-3-(phenylamino)-1-(phenylselenenyl)alkanes when submitted to similar reaction conditions. Bromoalkanes, functionalized in an analogous way, were obtained after hydrolytic workup when bromine was added to allylic benzimidates and tertiary benzamides. In some of these reactions, products of 6-endo cyclofunctionalization/hydrolysis (1-(benzoyloxy)-3-(phenylamino)-2-bromoalkanes) were also formed. The addition of benzeneselenenyl bromide to some a-substituted allylic benzimidates and tertiary benzamides was diastereoselective (0 < de < 90%, depending on conditions) with a preference for threo isomer formation. Hydrodeselenation/hydrodebromination of the cyclofunctionalization/hydrolysis products was efficiently effected (88-100% yield) by treatment of the products with triphenyltin hydride in refluxing benzene containing a catalytic amount of azobis(isobutyronitrile). The proper choice of allylic benzimidate/tertiary benzamide allowed the preparation of amino alcohol derivatives in which the 1,2-orientation of the functional groups, relative to the carbon backbone, could be varied in a controlled and predictable manner. The regioflexibility of the process was demonstrated for primary, secondary, and tertiary positions. When allylic benzamidines were submitted to the cyclofunctionalization/hydrolysis reaction conditions using benzeneselenenyl bromide as the electrophilic reagent, 5-phenylselenenyl(methyl) -substituted dihydroimidazoles were obtained.