1,3-diphenyl-1-nonanone | 136863-32-6

• 分子结构分类: 有机化合物 - 木脂素、新木脂素和相关化合物
• 英文名称: 1,3-diphenyl-1-nonanone
• 英文别名: 1,3-Diphenylnonan-1-one
• CAS: 136863-32-6
• 化学式: C₂₁H₂₆O
• 分子量: 294.437
• InChiKey: LOAAESJTQKLDQE-UHFFFAOYSA-N

物化性质

• 熔点：
  51-52 °C
• 沸点：
  423.7±24.0 °C(Predicted)
• 密度：
  0.988±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.5
• 重原子数：
  22
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  反式-查耳酮 在 copper(I) bromide dimethylsulfide complex hexylzirconocene 作用下， 以 四氢呋喃 为溶剂， 反应 0.17h， 以37%的产率得到1,3-diphenyl-1-nonanone
  参考文献：
  名称：

  铜催化的有机锆茂的共轭加成。综合和机理研究。

  摘要：

  在3–10 mol％的Cu（l）盐（例如CuBr·S Me 2或CuCN）存在下，烷基锆茂金属很容易添加到α，β-不饱和酮，醛和砜中。反应产率对路易斯酸和碱的存在敏感。在共轭加成过程中可以耐受立体位阻以及广泛的官能团。不饱和氮-酰基恶唑烷酮类对形成新的不对称碳具有高的非对映选择性。所得的烯醇锆可用于醛醇的串联醇醛加成反应。根据所用铜盐的类型，会发生缓慢或快速形成铜镜的现象，但是在光谱学上没有检测到中间的铜物种。因此，提出了一种机理，该机理涉及路易斯酸性的锆茂并烯的烯酮络合，然后烷基取代基的内球转移到螯合的Cu（l）上。

  DOI：

  10.1016/s0040-4020(01)85058-4

文献信息

• Tandem Addition β-Lithiation−Alkylation Sequence on α,β-Unsaturated Aldehydes
  作者：Norma Sbarbati Nudelman、Graciela V. García

  DOI：10.1021/jo005698d

  日期：2001.2.1

  isotopic exchange reactions and trapping of two intermediates, provide clues on the several mechanistic steps of this new reaction. Extended studies revealed that beta-alkyl-substituted alpha,beta-unsaturated aldehydes and aliphatic lithium reagents did not afford good yields of the tandem reaction products, while aromatic lithium reagents gave good results. The aggregation features of the aryllithium

  最近报道了（E）-肉桂醛1a与苯基锂之间的串联反应，得到β-取代的二氢查耳酮。反应混合物的NMR光谱研究以及同位素交换反应和两种中间体的捕集为该新反应的几个机理步骤提供了线索。扩展的研究表明，β-烷基取代的α，β-不饱和醛和脂肪族锂试剂不能提供串联反应产物的良好收率，而芳香族锂试剂则能提供良好的结果。芳基锂试剂的聚集特征和扩展的带电离域作用被认为可促进β-选择性。该方法为合成多种β-烷基取代的二氢查耳酮提供了便利的途径。
• Copper-catalyzed conjugate addition of in situ formed alkyl boranes to α,β-unsaturated ketones
  作者：Bernard Mravec、Kristína Plevová、Radovan Šebesta

  DOI：10.1007/s00706-018-2309-5

  日期：2019.2

  AbstractConjugate addition of in situ formed organometallic reagents to α,β-unsaturated carbonyl compounds provides an efficient way to generate new C–C bonds. We show optimization of the copper-catalyzed conjugate addition of alkylboranes, which were formed directly in the reaction mixture by hydroboration of alkenes. We have improved the reaction conditions by employing “greener”, less hygroscopic

  摘要将原位形成的有机金属试剂共轭添加到α，β-不饱和羰基化合物中提供了一种生成新C–C键的有效方法。我们展示了烷基硼烷的铜催化共轭加成的优化，烷基硼烷是通过烯烃的硼氢化直接在反应混合物中形成的。我们通过使用“更绿色”，更不易吸湿且沸点更高的溶剂2-甲基四氢呋喃改善了反应条件。我们还扩大了反应范围。此外，在中等对映选择性67:33 er的转化的对映选择性形式中，评估了手性二茂铁基卡宾配体 图形概要
• Transmetalation reactions of organosamarium reagents. Chlorosilane-accelerated copper-catalyzed conjugate additions
  作者：Peter Wipf、Srikanth Venkatraman

  DOI：10.1021/jo00064a040

  日期：1993.6

  TMSCl accelerates the conjugate addition of in situ prepared organosamarium reagents to alpha,beta-unsaturated carbonyl compounds and nitriles in the presence of HMPA and catalytic amounts of Cu(I) salts. Reactions at -78-degrees-C leads to silyl enol ethers which are isolated or cleaved with TBAF to give beta-alkylated ketones in 30-90% overall yield. Catalysis is most efficient in the presence of 4 equiv of TMSCl and HMPA. HMPA is also necessary for the in situ preparation of the organosamarium species from alkyl halide and SmI2. Some functional groups (chloride,ether,alkene, amide) are tolerated in this process. In the absence of Cu(I) salts, 1,2-additions of organosamarium reagents to carbonyl groups are also dramatically accelerated by TMSCl/HMPA and occur within minutes at -78-degrees-C.
• Transmetalation reactions of alkylzirconocenes: copper-catalyzed conjugate addition to enones
  作者：Peter Wipf、Jacqueline H. Smitrovich

  DOI：10.1021/jo00023a006

  日期：1991.11

  Rapid hydrozirconation of alkenes by zirconocene hydrochloride, followed by addition of 1 equiv of enone and catalytic amounts of Cu(I) salts, led to the corresponding 1,4-addition products in moderate to high yields and provided the first protocol for in situ preparation of alkyl cuprates from alkenes.
• Wipf Peter, Xu Wenjing, Smitrovich Jacqueline H., Lehmann Roman, Venanzi +, Tetrahedron, 50 (1994) N 7, S 1935-1954
  作者：Wipf Peter, Xu Wenjing, Smitrovich Jacqueline H., Lehmann Roman, Venanzi +

  DOI：——

  日期：——