1-丙酮,2-溴-1,2-二苯基- | 1832-41-3

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 中文名称: 1-丙酮,2-溴-1,2-二苯基-
• 英文名称: 2-bromo-1,2-diphenylpropan-1-one
• 英文别名: α-Brom-α-methyl-desoxybenzoin
• CAS: 1832-41-3
• 化学式: C₁₅H₁₃BrO
• 分子量: 289.172
• InChiKey: JNYGFWGPMBLNEX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-丙酮,2-溴-1,2-二苯基- 在 tris[(1S,2S,5S)-myrtanyl dimethyl]silane 、 四丁基氟化铵 作用下， 以 甲苯 为溶剂， 以30%的产率得到1,2-二(苯基)丙-1-酮
  参考文献：
  名称：

  [EN] CHIRAL ORGANOSILICON HYDRIDES
  [FR] HYDRURES DE COMPOSES ORGANOSILICIUM CHIRAUX

  摘要：

  该发明提供了一种用于对一个或多个电子给体基固定在该自由基的中心手性碳原子上，和/或固定在与中心手性碳原子相距1至4个原子的碳原子上的一个具有手性选择性还原的手性碳中心自由基的方法，包括在存在Lewis酸的情况下，用活化的手性非消旋有机硅氢化物处理所述自由基。该发明还提供了一种新型的活化手性非消旋有机硅氢化合物类。

  公开号：

  WO2004018487A1
• 作为产物：
  描述：

  1,2-二(苯基)丙-1-酮 在 三氯化铝 溴 作用下， 以 乙醚 为溶剂， 以95%的产率得到1-丙酮,2-溴-1,2-二苯基-
  参考文献：
  名称：

  Destabilized carbenium ions. Secondary and tertiary α-acetylbenzyl cations and α-benzoylbenzyl cations

  摘要：

  AbstractThe secondary α‐acetylbenzyl and α‐benzoylbenzyl cations, as well as their tertiary analogues, have been generated in a mass spectrometer by electron impact induced fragmentation of the corresponding α‐bromoketones. These ions belong to the interesting family of destabilized α‐acylcarbenium ions. While primary α‐acylcarbenium ions appear to be unstable, the secondary and tertiaiy ions exhibit the usual behaviour of stable entities in a potential energy well. This can be attributed to a ‘push‐pull’ substitution at the carbenium ion centre by an electron‐releasing phenyl group and an electron‐withdrawing acyl substituent. The characteristic unimolecular reaction of the metastaible secondary and tertiary α‐acylbenzyl cations is the elimination of CO by a rearrangement reaction involving a 1,2‐shift of a methyl group and a phenyl group, respectively. The loss of CO is accompanied by a very large kinetic energy release, which gives rise to broad and dish‐topped peaks for this process in the mass‐analysed ion kinetic energy spectra of the corresponding ions. This behaviour is attributed to the rigid critical configuration of a corner‐protonatei cyclopropanone derivative and a bridged phenonium ion derivative, respectively, for this reaction. For the tertiary α‐acetyl‐α‐methylbenzyl cations, it has been shown by deuterium labelling and by comparison of collisional activation spectra that these ions equilibrate prior to decomposition with their ‘protomer’ derivatives formed by proton migration from the α‐methyl substituent to the carbonyl group and to the benzene ring.

  DOI：

  10.1002/oms.1210220710

文献信息

• Catalytic Reductive Cross Coupling and Enantioselective Protonation of Olefins to Construct Remote Stereocenters for Azaarenes
  作者：Manman Kong、Yaqi Tan、Xiaowei Zhao、Baokun Qiao、Choon-Hong Tan、Shanshan Cao、Zhiyong Jiang

  DOI：10.1021/jacs.1c01073

  日期：2021.3.17

  A novel enantioselective protonation protocol that is triggered by reductive cross coupling of olefins is reported. When under cooperative photoredox and chiral hydrogen-bonding catalytic conditions and using a terminal reductant, various α-branched vinylketones with diverse vinylazaarenes could provide important enantioenriched azaarene derivatives containing tertiary stereocenters at their remote

  报道了一种由烯烃的还原交叉偶联触发的新型对映选择性质子化方案。当在协同光氧化还原和手性氢键催化条件下并使用末端还原剂时，具有不同乙烯基氮杂芳烃的各种α-支化乙烯基酮可以提供重要的对映体富集的氮杂芳烃衍生物，在其远端δ-位含有叔立体中心，具有高产率和对映选择性。该反应体系也适用于 α-支化的乙烯基氮杂芳烃，因此成功组装了难以捉摸的 1,4-立体中心。产物后期修饰方便，尤其是形成远程ε-叔碳和ε-杂四元碳立体中心，进一步凸显了该方法的重要合成价值。
• [EN] ORGANOGERMANIUM COMPOUNDS AND METHODS FOR THEIR USE<br/>[FR] COMPOSES D'ORGANOGERMANIUM ET PROCEDES D'UTILISATION DE CES COMPOSES
  申请人：CHIROGEN PTY LTD

  公开号：WO2004011473A1

  公开（公告）日：2004-02-05

  The invention provides a method for enantioselectively reducing a prochiral carbon centred radical having one or more electron donor groups attached directly to the central prochiral carbon atom of the radical, and/or attached to a carbon atom within 1 to 4 atoms of the central prochiral carbon atom, comprising treating said radical with a chiral non-racemic organogermanium hydride in the presence of a Lewis acid. The invention also provides a novel class of chiral non-racemic organogermanium hydrides and a method of preparing chiral non-racemic organogermanium compounds.

  该发明提供了一种对具有一个或多个直接连接到基本手性碳原子的自由基的顺对映选择性还原的方法，这些自由基具有一个或多个电子供体基团，和/或连接到中心手性碳原子周围1到4个原子内的碳原子上，包括在存在Lewis酸的情况下用手性非消旋有机锗氢化物处理所述自由基。该发明还提供了一类新型手性非消旋有机锗氢化物和制备手性非消旋有机锗化合物的方法。
• Synthesis, characterization and enantioselective free radical reductions of (1R,2S,5R)-menthyldiphenylgermane and its enantiomer
  作者：Le Zeng、Dainis Dakternieks、Andrew Duthie、Tamara Perchyonok、Carl Schiesser

  DOI：10.1016/j.tetasy.2004.06.020

  日期：2004.8

  5R)-Menthyldiphenylgermane and its enantiomer have been prepared in a few steps from germanium tetrachloride. The initial step in this sequence, namely the reaction between germanium tetrachloride and menthylmagnesium chloride, produces menthylgermanium trichloride, which is the exclusive product of this Grignard reaction, presumably due to the bulk of the menthyl group. When used at a low temperature

  （1 R，2 S，5 R）-甲基二苯基锗烷及其对映异构体是由四氯化锗分几步制备的。此顺序的第一步，即四氯化锗与氯化薄荷基镁之间的反应，产生了氯化三薄荷基锗，这是格氏试剂的唯一产物，可能是由于薄荷基的体积较大。当在低温（-78°C）下使用并与路易斯酸（如镁盐）结合使用时，这些手性锗烷能够以高对映选择性，但以中等产率收率还原酯官能化的自由基。例如，（R在镁存在下，于-78°C下于甲苯中将2-溴萘酚乙酯与（1 R，2 S，5 R）-薄荷基二苯基锗烷在甲苯中反应，可得到15％收率和99％ee的萘普生乙酯。溴化物。在80°C下，（1 R，2 S，5 R）-薄荷基二苯基锗烷与伯烷基自由基反应，速率常数为1.02×10 6  M -1  s -1。动力学研究表明该反应的Arrhenius表达式为：log（k / M -1  s -1）=（11.1±0.4）-（34.6±3.1）/ θ，其中θ = 2.3
• [EN] METHOD OF REMOVING ORGANOTIN RESIDUE<br/>[FR] PROCEDE POUR ELIMINER UN RESIDU D'ORGANOTINE
  申请人：CHIROGEN PTY LTD

  公开号：WO2004065334A1

  公开（公告）日：2004-08-05

  The invention provides a method of separating soluble organotin residue from a reduced product of a reduction reaction that uses an organotin hydride as a reducing agent, the method comprising: (i) contacting a reaction medium comprising said reduced product and soluble organotin residue with a substrate which, (a) is substantially insoluble in the reaction medium, (b) binds at least a portion of said soluble organotin residue, and (c) does not substantially bind the reduced product; (ii) separating said substrate from the reaction medium, thereby removing said at least a portion of organotin residue from the reaction medium; andrecovering the reaction medium comprising the reduced product. The invention also provides a method of performing a reduction reaction using an organotin hydride as a reducing agent that incorporates the method of separating soluble organotin residue.

  该发明提供了一种从使用有机锡氢化物作为还原剂的还原反应的还原产物中分离可溶性有机锡残留物的方法，该方法包括：(i)将包括所述还原产物和可溶性有机锡残留物的反应介质与底物接触，所述底物(a)在反应介质中基本不溶解，(b)结合至少部分可溶性有机锡残留物，(c)基本不结合还原产物；(ii)将所述底物从反应介质中分离，从而将至少部分有机锡残留物从反应介质中去除；并回收包括所述还原产物的反应介质。该发明还提供了一种使用有机锡氢化物作为还原剂进行还原反应的方法，其中包括分离可溶性有机锡残留物的方法。
• Boron Trifluoride Mediated Allylation of Aromatic α-Bromoketones by Allyltributyltin
  作者：Hideyoshi Miyake、Ryo Hirai、Yoshie Nakajima、Mitsuru Sasaki

  DOI：10.1246/cl.2003.164

  日期：2003.2

  Replacement of bromine atom of aromatic α-brormoketones by allyltributyltin in the presence of BF3 was described. The reaction proceeds with or without migration of the aryl group, depending on the structure of the α-bromoketone.

  描述了在BF3存在下，用烯丙基三丁基锡替换芳香族α-溴酮的溴原子。反应的进行是否伴随芳基团的迁移，取决于α-溴酮的结构。