2-(dibenzylamino)-1-phenylethanone | 24431-24-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-(dibenzylamino)-1-phenylethanone
• 英文别名: 2-(dibenzylamino)-1-phenylethan-1-one
• CAS: 24431-24-1
• 化学式: C₂₂H₂₁NO
• mdl: MFCD30223615
• 分子量: 315.415
• InChiKey: CVWYQQGHIHMOCF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  24
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.136
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-(dibenzylamino)-1-phenylethanone 在 palladium dihydroxide 盐酸 、 氢气 作用下， 以 甲醇 为溶剂， 反应 1.0h， 以85%的产率得到(+/-)-1-phenyl-2-(benzylamino)ethanol hydrochloride
  参考文献：
  名称：

  Stereocontrol between Remote Atom Centers in Acyclic Substrates. Anti Addition of Hydride to 1,5-, 1,6-, and 1,7-Hydroxy Ketones

  摘要：

  For conformationally unconstrained, acyclic organic compounds, the control of stereogenic centers at remote positions of a chain, that is, at a distance of four or more atom centers, remains a challenging problem in asymmetric synthesis. We report on our studies of 1,5, 1,6, and 1,7 diastereoselectivity in hydride reductions of acyclic hydroxy amino ketones and related compounds, which were sparked by our discovery of high 1,5 diastereocontrol (>10:1) with substrates such as 17 and 23. We have been able to achieve both high 1,5- and 1,6-anti diastereocontrol in the reduction of 1,5- and 1,6-hydroxy ketone substrates, respectively. However, the level of 1,7-anti diastereocontrol with 1,7-hydroxy ketones was only moderate. More specifically, reduction of 23 to 24 with R-alpine-hydride or Zn(BH4)(2) in CH2Cl2 (predominantly) at -78 degrees C gave high 1,5-anti stereoselectivity (anti/syn = 10:1 or 13:1, respectively), and reduction of 34 to 35 with R-alpine-hydride (CH2Cl2) gave high 1,6-anti selectivity (anti/syn = 12:1, respectively), whereas reduction of 46 to 44 with R-alpine-hydride (CH2Cl2) gave only moderate 1,7-anti stereoselectivity (anti/syn = 3:1). Results for reductions of 1,5- and 1,6-hydroxy ketone substrates having the N-benzyl structural subunit replaced (i.e., 27 --> 28, 29 --> 30, 31 --> 32, 52 --> 53, 54a --> 55a, 54b --> 55b, 54c --> 55c, and 56 --> 57) clearly indicate that the stereoelectronic character of this subunit plays a critical. role in the attainment of high anti asymmetric induction. Thus, while we obtained exceptionally high 1,6-anti stereoselectivity in the reduction of the N-mesitylmethyl substrate, 54c, to 1,6-diols 55c (anti/syn = 22:1) with R-alpine-hydride at -78 degrees C in CH2Cl2, the N-methyl substrate, 54b, gave a relatively modest anti/syn ratio of 3:1. The diminished anti/syn ratio of 4:1 in the R-alpine-hydride reduction of methoxy amino ketone 50 to 51 also indicates the importance of the free hydroxyl group for attaining high 1,6-anti stereoselectivity. To rationalize the high remote anti stereocontrol in such acyclic systems, we discuss a chelation-controlled mechanism, involving external hydride addition to a bicyclic metal complex with a coordinated ketone carbonyl (e.g., 33) vs internal hydride addition to a monocyclic metal complex with an uncoordinated ketone carbonyl (e.g., 58).

  DOI：

  10.1021/jo981341m
• 作为产物：
  描述：

  2,2-二氯苯乙酮 以 乙醚 为溶剂， 150.0~155.0 ℃ 、1.33 Pa 条件下， 生成 2-(dibenzylamino)-1-phenylethanone
  参考文献：
  名称：

  α-酮醛的氨基和半氨基 43. α-卤代胺的通讯

  摘要：

  半缩醛 4 由 α-酮醛 1 和 1 摩尔仲胺形成，通过脱氢转化为乙醛酰胺 6。胺 5 可通过 α-酮醛 1 与 2 mol 的缩合获得，或通过 α, α-二氯酮 2 与 4 mol 的仲胺反应得到；它们被乙酰氯裂解得到 α-卤代胺 8。α, α-二氯丙酮和 2 摩尔二甲胺或哌啶的缩合产生 1-氨基-3-二氯甲基-2-丁烯-1-甲酰胺 16 的衍生物。

  DOI：

  10.1002/ardp.19733060309

文献信息

• Stereodivergent Nucleophilic Additions to Racemic β-Oxo Acid Derivatives: Fast Addition Outcompetes Stereoconvergence in the Archetypal Configurationally Unstable Electrophile
  作者：Pedro De Jesús Cruz、Evan T. Crawford、Shubin Liu、Jeffrey S. Johnson

  DOI：10.1021/jacs.1c07702

  日期：2021.10.6

  Additions of carbon nucleophiles to racemic α-stereogenic β-oxo acid derivatives that deliver enantiomerically enriched tertiary alcohols are valuable, but uncommon. This article describes stereodivergent Cu-catalyzed borylative cyclizations of racemic β-oxo acid derivatives bearing tethered pro-nucleophilic olefins to deliver highly functionalized cyclopentanols containing four contiguous stereogenic

  将碳亲核试剂添加到外消旋 α-立体 β-氧代酸衍生物中，以提供对映异构体富集的叔醇是有价值的，但并不常见。本文描述了带有束缚前亲核烯烃的外消旋 β-氧代酸衍生物的立体发散 Cu 催化的硼化环化，以提供含有四个连续立体中心的高度官能化的环戊醇。报告的协议适用于一系列β-含氧酸衍生物，并且非对映体产物很容易通过典型的色谱技术分离。α-立体-β-酮酯通常被认为具有极端或自发的构型脆性，
• Ultrafast Iron-Catalyzed Reduction of Functionalized Ketones: Highly Enantioselective Synthesis of Halohydrines, Oxaheterocycles, and Aminoalcohols
  作者：Clemens K. Blasius、Vladislav Vasilenko、Lutz H. Gade

  DOI：10.1002/anie.201806196

  日期：2018.8.6

  A molecularly defined chiral boxmi iron alkyl complex catalyzes the hydroboration of various functionalized ketones and provides the corresponding chiral halohydrines, oxaheterocycles (oxiranes, oxetanes, tetrahydrofurans, and dioxanes) and amino alcohols with excellent enantioselectivities (up to >99 %ee) and conversion efficiencies at low catalyst loadings (as low as 0.5 mol %). Turnover frequencies

  分子定义的手性boxmi铁烷基络合物催化各种官能化酮的氢硼化，并提供相应的手性卤代醇，氧杂杂环（环氧乙烷，氧杂环丁烷，四氢呋喃和二恶烷）和氨基醇，具有出色的对映选择性（高达> 99％ee）和转化效率在低催化剂负载量（低至0.5 mol％）下。在−30°C时，周转频率大于40000 h -1突显了这种富含地球的金属催化剂的活性，该催化剂可耐受许多官能团。
• Preparation and facile addition reactions of iminium salts derived from amino ketene silyl acetal and amino silyl enol ether
  作者：Makoto Shimizu、Shingo Hata、Koichi Kondo、Kazuhiro Murakami、Isao Mizota、Yusong Zhu

  DOI：10.1039/d0ra05768a

  日期：——

  While iminium salts generated by the oxidation of amino ketene silyl acetals show intriguing reactivities to give useful γ-oxo-α-amino esters via reactions with silyl enol ethers in good yields, new iminium salts are also prepared by the oxidation of amino silyl enol ethers. They undergo facile addition reaction with various nucleophiles to give α-amino ketone derivatives in good yields.

  虽然由氨基烯酮甲硅烷基缩醛氧化生成的亚胺盐显示出有趣的反应性，可通过与甲硅烷基烯醇醚反应以良好收率产生有用的 γ-氧代-α-氨基酯，但也可通过氨基甲硅烷基烯醇醚的氧化制备新的亚胺盐. 它们与各种亲核试剂进行容易的加成反应，以良好的收率得到 α-氨基酮衍生物。
• Synthesis of α-Amino Acids by Umpolung of Weinreb Amide Enolates
  作者：Sebastian Hirner、Donata K. Kirchner、Peter Somfai

  DOI：10.1002/ejoc.200800683

  日期：2008.11

  An efficient and diastereoselective synthesis of alpha-amino acids from readily available starting materials has been developed. The key feature of this reaction is an umpolung of a glycine-derived ...

  已经开发出一种从容易获得的起始材料高效和非对映选择性合成 α-氨基酸的方法。该反应的主要特征是甘氨酸衍生的...
• Oxidative Amination of Aldehydes with Amines into α-Amino Ketones
  作者：Jie-Sheng Tian、Shuang-Wen Xu、Yan-Hang Bi、Zhan-Zhi Cao、Teck-Peng Loh

  DOI：10.1021/acs.orglett.3c03771

  日期：2023.12.15

  Oxidative amination for the installation of nitrogen functional molecules from nitrogen nucleophiles has always been a very challenging topic in organic synthesis. Here we report a novel conversion of different aldehydes with secondary amines for the synthesis of diversified α-amino ketones. This method can be achieved through oxidative rearrangement of an in situ-generated enamine intermediate promoted

  从氮亲核试剂中安装氮功能分子的氧化胺化一直是有机合成中非常具有挑战性的课题。在这里，我们报道了不同醛与仲胺的新型转化，用于合成多样化的 α-氨基酮。该方法可以通过由市售的过碳酸钠促进的原位生成的烯胺中间体的氧化重排来实现。此外，这种一锅法也适用于复杂分子的功能修饰。