methyl (3E,5E)-2-diazo-6-phenylhexa-3,5-dienoate | 161260-51-1

• 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: methyl (3E,5E)-2-diazo-6-phenylhexa-3,5-dienoate
• CAS: 161260-51-1
• 化学式: C₁₃H₁₂N₂O₂
• 分子量: 228.25
• InChiKey: JUZFZSJAAOYHSW-NXZHAISVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  28.3
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1,3-环己二烯 、 methyl (3E,5E)-2-diazo-6-phenylhexa-3,5-dienoate 在 Rh₂((S)-N-(dodecylbenzenesulfonyl)prolinate)4 作用下， 以 正己烷 为溶剂， 以60%的产率得到methyl (2E,5E)-4-(2,5-cyclohexadienyl)-6-phenyl-2,5-hexadienoate
  参考文献：
  名称：

  Catalytic Asymmetric Synthesis of Diarylacetates and 4,4-Diarylbutanoates. A Formal Asymmetric Synthesis of (+)-Sertraline

  摘要：

  The intermolecular C-H insertion chemistry of phenyldiazoacetates catalyzed by dirhodium tetrakis((S)-N (dodecylbenzenesulfonyl)prolinate) (Rh-2(S-DOSP)(4)) can be effectively carried out on cyclohexadienes, leading to the asymmetric synthesis of diarylacetates. The reaction of vinyldiazoacetates with cyclohexadienes results in an unprecedented carbenoid reaction that is formally a combined C-H insertion/Cope rearrangement. The synthetic utility of this novel transformation was demonstrated by its utilization in a formal asymmetric synthesis of (+)-sertraline.

  DOI：

  10.1021/ol9905699
• 作为产物：
  描述：

  Methyl (E,E)-6-phenylhexa-3,5-dienoate 在 4-乙酰氨基苯磺酰叠氮 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 乙腈 为溶剂， 生成 methyl (3E,5E)-2-diazo-6-phenylhexa-3,5-dienoate
  参考文献：
  名称：

  铑（II）-乙烯基类胡萝卜素插入SiH键中。烯丙基硅烷的立体定向合成的新方法

  摘要：

  在有机硅烷的存在下，Rh 2（OAc）4催化的乙烯基重氮羰基化合物的分解立体定向地以良好的收率生成了相应的烯丙基硅烷。还考虑了不对称方法，以及将方法扩展到其他烯丙基系统的合成。

  DOI：

  10.1016/0040-4039(94)88508-7

文献信息

• C−H Activation as a Strategic Reaction:  Enantioselective Synthesis of 4-Substituted Indoles
  作者：Huw M. L. Davies、James R. Manning

  DOI：10.1021/ja057768+

  日期：2006.2.1

  A method is described for the asymmetric synthesis of 4-substituted indoles from the Rh2(S-DOSP)4-catalyzed decomposition of vinyldiazoacetates in the presence of N-Boc-4-acetoxy-6,7-dihydroindole. The reaction proceeds via a combined C-H activation/Cope rearrangement-elimination mechanism resulting in good yields and very high asymmetric induction.

  描述了在 N-Boc-4-乙酰氧基-6,7-二氢吲哚存在下，从 Rh2(S-DOSP)4 催化的重氮乙酸乙烯酯分解不对称合成 4-取代吲哚的方法。该反应通过组合的 CH 活化/Cope 重排 - 消除机制进行，导致良好的产率和非常高的不对称诱导。
• Access to N-Substituted 2-Pyridones by Catalytic Intermolecular Dearomatization and 1,4-Acyl Transfer
  作者：Guangyang Xu、Ping Chen、Pei Liu、Shengbiao Tang、Xinhao Zhang、Jiangtao Sun

  DOI：10.1002/anie.201812937

  日期：2019.2.11

  A novel rhodium‐catalyzed dearomatization of O‐substituted pyridines to access N‐substituted 2‐pyridones has been developed. A computational study suggests a mechanism involving the formation of a pyridinium ylide followed by an unprecedented 1,4‐acyl migratory rearrangement from O to C. Furthermore, the chiral dirhodium complexes serve as the catalyst for the asymmetric transformation with excellent

  已经开发出了一种新型的O取代吡啶铑催化脱芳香化剂，以得到N取代的2-吡啶酮。一项计算研究表明，该机理涉及吡啶鎓叶立德的形成，然后发生前所未有的从O到C的1,4-酰基迁移重排。此外，手性吡啶鎓配合物可作为不对称转化的催化剂，并具有出色的对映选择性控制。DFT计算表明手性从轴向手性转移到中央立体中心。较强的π-π相互作用和CH-π相互作用说明了高对映选择性。
• Rhodium(II) (S)-N-(arylsulfonyl)prolinate catalyzed asymmetric insertions of vinyl- and phenylcarbenoids into the SiH bond
  作者：Huw M.L. Davies、Tore Hansen、James Rutberg、Paul R. Bruzinski

  DOI：10.1016/s0040-4039(97)00205-0

  日期：1997.3

  Allylsilanes or benzylsilanes of high enantiomeric purity (77–95% ee) are formed from the rhodium(II) (S)-N-[p-(dodecylphenyl)sulfonyl]prolinate (1) catalyzed decomposition of vinyldiazomethanes or phenyldiazomethanes in the presence of dimethylphenylsilane (3).

  烯丙基硅烷或高对映体纯度（77-95％ee）的的benzylsilanes从铑（II）（S）-N-形成[对- （十二烷基苯基）磺酰基]脯氨酸（1）在存在或vinyldiazomethanes的phenyldiazomethanes催化分解二甲基苯基硅烷（3）。
• A Stereospecific Access to Allylic Systems Using Rhodium(II)−Vinyl Carbenoid Insertion into Si−H, O−H, and N−H Bonds
  作者：Priyadarshanie Bulugahapitiya、Yannick Landais、Liliana Parra-Rapado、Denis Planchenault、Valéry Weber

  DOI：10.1021/jo961952j

  日期：1997.3.1

  Rhodium-catalyzed decomposition of alpha-vinyldiazoesters in the presence of silanes, alcohols, ethers, amines, and thiols have been shown to produce the corresponding alpha-silyl, alpha-hydroxy, alpha-alkoxy, alpha-amino, and alpha-thioalkoxy esters in generally good yield with a complete retention of the stereochemistry of the double bond of the diazo precursor. An extension of the process in homochiral series has also been devised using either a chiral auxiliary attached to the ester function or achiral alpha-vinyldiazoesters and Doyle's chiral catalyst Rh-2(MEPY)(4). In the former approach, pantolactone as chiral auxiliary gave diastereoselectivities of up to 70%, while the second approach produced the desired allylsilane with ee as high as 72%. On the other hand, Rh-2(MEPY)(4)-catalyzed insertion into the O-H bond of water led to poor or no enantioselectivity in good agreement with recent literature reports.
• Catalytic Asymmetric Reactions for Organic Synthesis:  The Combined C−H Activation/Siloxy-Cope Rearrangement
  作者：Huw M. L. Davies、Rohan E. J. Beckwith

  DOI：10.1021/jo048429m

  日期：2004.12.1

  Tetrakis(N-[4-dodecylbenzenesulfonyl]-(L)-prolinate) dirhodium [Rh-2(S-DOSP)(4)]-catalyzed decomposition of vinyldiazoacetates in the presence of allyl silyl ethers results in the formation of the direct C-H insertion product and the product derived from a combined C-H activation/siloxy-Cope rearrangement. Both products are formed with very high diastereoselectivity (>94% de) and high enantioselectvity (78-93% ee). Under thermal or microwave conditions, the direct C-H insertion product undergoes a siloxy-Cope rearrangement in a stereoselective manner.