3,6-dimethyl-2,4-heptanedione | 83631-16-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3,6-dimethyl-2,4-heptanedione
• 英文别名: 3,6-dimethylheptan-2,4-dione；3,6-Dimethylheptane-2,4-dione
• CAS: 83631-16-7
• 化学式: C₉H₁₆O₂
• 分子量: 156.225
• InChiKey: BEWPTSWPIROTRC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  11
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3,6-dimethyl-2,4-heptanedione 、 过氧化苯甲酰 在 2,6-二叔丁基-4-甲基苯酚 、 (S)-N1,N1-diethyl-3,3-dimethylbutane-1,2-diamine trifluoromethanesulfonate 作用下， 以 氯仿 为溶剂， 以60%的产率得到
  参考文献：
  名称：

  Asymmetric α-Benzoyloxylation of β-Ketocarbonyls by a Chiral Primary Amine Catalyst

  摘要：

  The direct asymmetric α-benzoyloxylation of β-ketocarbonyls catalyzed by a chiral primary amine is described herein. This protocol demonstrates excellent enantioselectivity for a broad range of substrates, which allows convenient access to highly enantioenriched α-hydroxy-β-ketocarbonyls.

  DOI：

  10.1021/ol503592n
• 作为产物：
  描述：

  异戊醛 在 sodium hydroxide 作用下， 以 乙醚 、 水 、 丙酮 为溶剂， 反应 24.0h， 生成 3,6-dimethyl-2,4-heptanedione
  参考文献：
  名称：

  The isolation, identification and synthesis of 3,6-dimethylheptan-2,4-dione, a pheromone of the mushroom fly, Megaselia halterata (diptera:phoridae)

  摘要：

  DOI：

  10.1016/s0040-4039(00)87544-9

文献信息

• Asymmetric α-Alkylation of β-Ketocarbonyls via Direct Phenacyl Bromide Photolysis by Chiral Primary Amine
  作者：Wenzhao Zhang、Yunbo Zhu、Long Zhang、Sanzhong Luo

  DOI：10.1002/cjoc.201800125

  日期：2018.8

  Enantioselective α‐photoalkylation of β‐ketocarbonyls without any external photosensitizer was described in this work. The photoalkylation reactions, enabled solely by a chiral primary amine catalyst, provided convenient constructions of all‐carbon quaternary stereocenters with good activity and high enantioselectivity. Mechanism studies revealed a direct photolytic radical chain process under visible

  这项工作描述了β-酮羰基的对映选择性α-光烷基化反应，而没有任何外部光敏剂。仅通过手性伯胺催化剂就能进行的光烷基化反应，可以方便地构建具有良好活性和高对映选择性的全碳四元立体中心。机理研究表明在可见光照射下有直接的光解自由基链过程。
• Asymmetric α-Photoalkylation of β-Ketocarbonyls by Primary Amine Catalysis: Facile Access to Acyclic All-Carbon Quaternary Stereocenters
  作者：Yunbo Zhu、Long Zhang、Sanzhong Luo

  DOI：10.1021/ja508605a

  日期：2014.10.22

  We describe the direct construction of all-carbon quaternary stereocenters via α-photoalkylation of β-ketocarbonyls with high efficacy and enantioselectivities by merging photoredox catalysis and primary amine catalysis. The open-shell photoradical approach enables asymmetric α-alkylations that are difficult under thermal conditions.

  我们描述了通过合并光氧化还原催化和伯胺催化，通过具有高效和对映选择性的 β-酮羰基的 α-光烷基化直接构建全碳四元立体中心。开壳光自由基方法能够实现在热条件下难以实现的不对称 α-烷基化。
• Enantioselective Terminal Addition to Allenes by Dual Chiral Primary Amine/Palladium Catalysis
  作者：Han Zhou、Yaning Wang、Long Zhang、Mao Cai、Sanzhong Luo

  DOI：10.1021/jacs.7b00437

  日期：2017.3.15

  We herein describe a synergistic chiral primary amine/achiral palladium catalyzed enantioselective terminal addition to allenes with α-branched β-ketocarbonyls and aldehydes. The reactions afford allylic adducts bearing acyclic all-carbon quaternary centers with high regio- and enantioselectivity. A wide range of allenes including those aliphatic or 1,1'-disubstituted could be employed, thus expanding

  我们在此描述了一种协同手性伯胺/手性钯催化的对映选择性末端加成到具有 α-支链 β-酮羰基和醛的丙二烯。该反应提供具有高区域选择性和对映选择性的具有无环全碳四元中心的烯丙基加合物。可以使用广泛的丙二烯，包括脂肪族或 1,1'-二取代的丙二烯，从而扩展了典型的不对称烯丙基烷基化反应的范围。
• Asymmetric Retro-Claisen Reaction by Chiral Primary Amine Catalysis
  作者：Yunbo Zhu、Long Zhang、Sanzhong Luo

  DOI：10.1021/jacs.6b00627

  日期：2016.3.30

  The communication describes an enamine-based asymmetric retro-Claisen reaction of β-diketones by primary amine catalysis. The reaction proceeds via a sequence of stereoselective C-C formation, C-C cleavage, and a highly stereospecific enamine protonation to afford chiral α-alkylated ketones or macrolides with high yields and enantioselectivities. A detailed mechanism was explored on the basis of experimental

  该通讯描述了伯胺催化下 β-二酮的基于烯胺的不对称逆克莱森反应。该反应通过一系列立体选择性 CC 形成、CC 裂解和高度立体有择的烯胺质子化进行，以提供具有高产率和对映选择性的手性 α-烷基化酮或大环内酯。在实验证据和计算研究的基础上探索了详细的机制，以解释观察到的立体控制。
• Catalytic Asymmetric Mannich Reaction with N-Carbamoyl Imine Surrogates of Formaldehyde and Glyoxylate
  作者：Yang'en You、Long Zhang、Linfeng Cui、Xueling Mi、Sanzhong Luo

  DOI：10.1002/anie.201707005

  日期：2017.10.23

  N,O‐acetals (NOAcs) were developed as bench stable surrogates for N‐carbamoyl, (Boc, Cbz and Fmoc) formaldehyde and glyoxylate imines in asymmetric Mannich reactions. The NOAcs can be directly utilized in the chiral primary amine catalyzed Mannich reactions of both acyclic and cyclic β‐ketocarbonyls with high yields and excellent stereoselectivity. The current reaction offers a straightforward approach

  N，O-乙缩醛（NOAcs）是作为不对称曼尼希反应中N-氨基甲酰基（Boc，Cbz和Fmoc）甲醛和乙醛酸亚胺的替补稳定替代物而开发的。NOAcs可直接用于无环和环状β-酮羰基的手性伯胺催化的曼尼希反应中，具有高收率和出色的立体选择性。当前的反应提供了一种直接且可行的方法，以实用且高度立体控制的方式不对称合成带有手性季中心的α-或β-氨基羰基。