1-deutero-1,3-diphenylprop-2-yn-1-ol

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 直链 1,3-二芳基丙烷
• 英文名称: 1-deutero-1,3-diphenylprop-2-yn-1-ol
• 英文别名: (E)-1-deutero-1,3-diphenylprop-2-en-1-ol；(E)-1,3-diphenylprop-2-en-[1-2H]-1-ol；(E)-1-deuterio-1,3-diphenylprop-2-en-1-ol
• 化学式: C₁₅H₁₄O
• 分子量: 211.268
• InChiKey: ORACYDGVNJGDMI-VDRRKQHSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-deutero-1,3-diphenylprop-2-yn-1-ol 在 1,10-菲罗啉 、 sodium t-butanolate 作用下， 以 甲苯 为溶剂， 反应 36.0h， 生成 ω-苄基苯乙酮
  参考文献：
  名称：

  Transition-Metal-Free Self-Hydrogen-Transferring Allylic Isomerization

  摘要：

  Phenanthroline and tert-butoxide have been established as powerful radical initiators in reactions such as the S(RN)1-type coupling reactions due to the cooperation of large heteroarenes and a special feature of tert-butoxide. The first phenanthroline-tert-butoxide-catalyzed transition-metal-free allylic isomerization is described. The resulting ketones are key intermediates for indenes. The control experiments rule out the base-promoted allylic anion pathway. The radical pathway is supported by experimental evidence that includes kinetic study, kinetic isotope effect, isotope-labeling experiments, trapping experiments, and EPR experiments.

  DOI：

  10.1021/acs.orglett.5b03124
• 作为产物：
  描述：

  (2E)-1-phenyl-3-[4-(trifluoromethyl)phenyl]prop-2-en-1-one 在 1,10-菲罗啉 、 硼氘化钠 、 cerium(III) chloride heptahydrate 、 sodium t-butanolate 作用下， 以 甲醇 、 甲苯 为溶剂， 反应 3.0h， 生成 1-deutero-1,3-diphenylprop-2-yn-1-ol
  参考文献：
  名称：

  Transition-Metal-Free Self-Hydrogen-Transferring Allylic Isomerization

  摘要：

  Phenanthroline and tert-butoxide have been established as powerful radical initiators in reactions such as the S(RN)1-type coupling reactions due to the cooperation of large heteroarenes and a special feature of tert-butoxide. The first phenanthroline-tert-butoxide-catalyzed transition-metal-free allylic isomerization is described. The resulting ketones are key intermediates for indenes. The control experiments rule out the base-promoted allylic anion pathway. The radical pathway is supported by experimental evidence that includes kinetic study, kinetic isotope effect, isotope-labeling experiments, trapping experiments, and EPR experiments.

  DOI：

  10.1021/acs.orglett.5b03124

文献信息

• Dirhodium(<scp>ii</scp>)/P(<i>t</i>-Bu)₃ catalyzed tandem reaction of α,β-unsaturated aldehydes with arylboronic acids
  作者：Ziling Ma、Yuanhua Wang

  DOI：10.1039/c8ob01997e

  日期：——

  catalyst for the synthesis of aryl alkyl ketones by the tandem reaction of α,β-unsaturated aromatic or aliphatic aldehydes with arylboronic acids. This tandem procedure included arylation followed by the isomerization reaction. This method exhibits good functional group tolerance and has a broad substrate scope. With the conjugated aldehydes, the one-step synthesis of γ,δ-unsaturated ketones was realized

  提倡将膦连接的乙酸二铑（II）用作通过α，β-不饱和芳族或脂族醛与芳基硼酸的串联反应合成芳基烷基酮的催化剂。该串联过程包括芳基化，然后进行异构化反应。该方法表现出良好的官能团耐受性并且具有广泛的底物范围。通过共轭醛，通过该反应实现了γ，δ-不饱和酮的一步合成。值得注意的是，Rh-P键的长度是影响催化反应的重要因素。轴向烷基膦与芳基膦连接的二吡啶（II）晶体结构的比较分析）乙酸盐表明，与较长的Rh-P键相比，较短的Rh-P键长度有利于异构化过程。另外，反应完成后可以回收二吡啶（II）化合物。
• Oxygenation of Simple Olefins through Selective Allylic C−C Bond Cleavage: A Direct Approach to Cinnamyl Aldehydes
  作者：Jianzhong Liu、Xiaojin Wen、Chong Qin、Xinyao Li、Xiao Luo、Ao Sun、Bencong Zhu、Song Song、Ning Jiao

  DOI：10.1002/anie.201705671

  日期：2017.9.18

  allylic C−C σ‐bond cleavage of simple olefins to give valuable cinnamyl aldehydes is reported. 1,2‐Aryl or alkyl migration through allylic C−C bond cleavage occurs in this transformation, which is assisted by an alkyl azide reagent. This method enables O‐atom incorporation into simple unfunctionalized olefins to construct cinnamyl aldehydes. The reaction features simple hydrocarbon substrates, metal‐free

  据报道，一种新颖的不含金属的烯丙基CCσ键裂解简单的烯烃可得到有价值的肉桂醛。1,2-芳基或烷基迁移通过烯丙基C-C键断裂在此转化过程中发生，这需要烷基叠氮化物试剂的协助。这种方法可以使O-atom掺入简单的未官能化烯烃中，以构建肉桂醛。该反应具有简单的烃底物，无金属条件以及高区域选择性和立体选择性。
• Base-Mediated Cascade Rearrangements of Aryl-Substituted Diallyl Ethers
  作者：Jolene P. Reid、Catherine A. McAdam、Adam J. S. Johnston、Matthew N. Grayson、Jonathan M. Goodman、Matthew J. Cook

  DOI：10.1021/jo502403n

  日期：2015.2.6

  Two base-mediated cascade rearrangement reactions of diallyl ethers were developed leading to selective [2,3]-Wittig–oxy-Cope and isomerization–Claisen rearrangements. Both diaryl and arylsilyl-substituted 1,3-substituted propenyl substrates were examined, and each exhibits unique reactivity and different reaction pathways. Detailed mechanistic and computational analysis was conducted, which demonstrated

  开发了两个碱基介导的二烯丙基醚的级联重排反应，从而导致选择性的[2,3] -Wittig-oxy-Cope和异构化-Claisen重排。对二芳基和芳基甲硅烷基取代的1,3-取代的丙烯基底物均进行了检测，每种底物均具有独特的反应性和不同的反应途径。进行了详细的机理和计算分析，表明碱和溶剂的作用是观察到的反应性和选择性的关键。交叉实验还表明，这些反应以一定程度的解离进行，并且机理途径是高度复杂的，具有多种竞争途径。