trans-3,5-dimethylcyclohexanone

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: trans-3,5-dimethylcyclohexanone
• 英文别名: trans-3,5-Dimethyl-cyclohexanon；(3S,5S)-3,5-dimethylcyclohexan-1-one
• 化学式: C₈H₁₄O
• 分子量: 126.199
• InChiKey: MSANHHHQJYQEOK-BQBZGAKWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.88
• 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：

  trans-3,5-dimethylcyclohexanone 在 间氯过氧苯甲酸 作用下， 以 甲苯 为溶剂， 反应 6.0h， 生成 (2S,5R,7R)-5,7-Dimethyl-2-((R)-1-phenyl-ethyl)-1-oxa-2-aza-spiro[2.5]octane
  参考文献：
  名称：

  Structural Analysis of .beta.-Turn Mimics Containing a Substituted 6-Aminocaproic Acid Linker

  摘要：

  A series of beta-turn models have been prepared consisting of the dipeptide Ala-Gly cyclized with all stereoisomers of 6-amino-3,5-dimethylcaproic acid and 6-amino-3-methylcaproic acid, as were related peptides based on Gly-Gly and Ala-Ala, The requisite linkers were made using routes featuring stereoselective ring-expansion reactions and the syntheses completed using standard methodology. A preliminary examination of these compounds has been carried out using NMR spectroscopy, circular dichroism, and, in several cases, X-ray crystallography. These studies indicate that, depending on linker stereochemistry, different proportions of type II and type I turns were observed in solution. Both type I and type II turns were observed in the solid state.

  DOI：

  10.1021/ja00124a001
• 作为产物：
  描述：

  methyl 5-methyl-3-oxo-6-octenoate 在 双(乙腈)氯化钯(II) 三甲基氯硅烷 、 copper dichloride 作用下， 以 1,4-二氧六环 为溶剂， 生成 trans-3,5-dimethylcyclohexanone
  参考文献：
  名称：

  在氯代三甲基硅烷存在下，钯催化的烯基β-酮酯环化反应。

  摘要：

  在化学计量的SiMe3Cl存在下，PdCl2（CH3CN）2催化了烯基β-酮酯的环化反应，从而以高收率和极佳的区域选择性形成了2-羰基烷氧基环己酮。

  DOI：

  10.1039/b111644d

文献信息

• A Scalable Synthesis of (<i>R</i>,<i>R</i>)-2,6-Dimethyldihydro-2<i>H</i>-pyran-4(3<i>H</i>)-one
  作者：Ian S. Young、Matthew W. Haley、Annie Tam、Steven A. Tymonko、Zhongmin Xu、Ronald L. Hanson、Animesh Goswami

  DOI：10.1021/op500135x

  日期：2015.10.16

  Kulinkovich cyclopropanation of silyl protected (R)-ethyl 3-hydroxybutanoate, and subsequent oxidative fragmentation of the cyclopropanol. The resulting vinyl ketone intermediate was then subjected to oxidative Heck cyclization to form the enone substrate required for conjugate addition. A diastereoselective copper-catalyzed Grignard addition procedure was implemented to install the requisite methyl

  报道了（R，R）-2,6-二甲基二氢-2 H-吡喃-4（3 H）-one的可扩展合成。该策略的关键是Ti（O i Pr）4催化的甲硅烷基保护的Kulinkovich环丙烷化（R）-3-羟基丁酸乙酯，随后环丙醇的氧化裂解。然后将所得的乙烯基酮中间体进行氧化Heck环化反应以形成共轭物添加所需的烯酮底物。实施了非对映选择性铜催化的格氏试剂加成步骤，以安装必需的甲基，其中包括1,3-双（二苯基膦基）丙烷和三甲基甲硅烷基氯，大大提高了该方法的耐用性。
• METHOD FOR SYNTHESIZING OPTICALLY ACTIVE CARBONYL COMPOUNDS
  申请人：BASF SE

  公开号：US20180057437A1

  公开（公告）日：2018-03-01

  The present invention relates to a process for the preparation of an optically active carbonyl compound by asymmetric hydrogenation of a prochiral α,β-unsaturated carbonyl compound with hydrogen in the presence of at least one optically active transition metal catalyst that is soluble in the reaction mixture and which has rhodium as catalytically active transition metal and a chiral, bidentate bisphosphine ligand, wherein the reaction mixture during the hydrogenation of the prochiral α,β-unsaturated carbonyl compound additionally comprises at least one compound of the general formula (I): in which R 1 , R 2 : are identical or different and are C 6 - to C 10 -aryl which is unsubstituted or carries one or more, e.g. 1, 2, 3, 4 or 5, substituents which are selected from C 1 - to C 6 -alkyl, C 3 - to C 6 -cycloalkyl, C 6 - to C 10 -aryl, C 1 - to C 6 -alkoxy and amino; Z is a group CHR 3 R 4 or aryl which is unsubstituted or carries one or more, e.g. 1, 2, 3, 4 or 5, substituents which are selected from C 1 - to C 6 -alkyl, C 3 - to C 6 -cycloalkyl, C 6 - to C 10 -aryl, C 1 - to C 6 -alkoxy and amino, wherein R 3 and R 4 are as defined in the claims and the description.

  本发明涉及一种通过在至少一种可溶于反应混合物中的光学活性过渡金属催化剂的存在下，将可溶性光学活性过渡金属铑和手性双膦配体作为催化活性过渡金属的α，β-不对称氢化的可半手性α，β-不饱和羰基化合物与氢气反应制备光学活性羰基化合物的方法。在氢化可半手性α，β-不饱和羰基化合物的过程中，反应混合物中还包括至少一种符合一般式（I）的化合物：其中 R1、R2：相同或不同，为未取代或带有一个或多个（例如1、2、3、4或5个）C6到C10芳基取代基的化合物，所述取代基选自C1到C6烷基、C3到C6环烷基、C6到C10芳基、C1到C6烷氧基和氨基；Z是一种基团CHR3R4或未取代或带有一个或多个（例如1、2、3、4或5个）取代基的芳基，所述取代基选自C1到C6烷基、C3到C6环烷基、C6到C10芳基、C1到C6烷氧基和氨基，其中R3和R4如权利要求和说明书中定义。
• Central nervous system active compounds. III. The synthesis of 4- and 6-substituted caprolactam derivatives by the Schmidt and Beckmann rearrangements
  作者：GI Hutchison、RH Prager、AD Ward

  DOI：10.1071/ch9802477

  日期：——

  The synthesis is described of hexahydroazepin-2-ones (caprolactams) bearing 1-4 alkyl or aryl groups at C4 and C6 by the Beckmann or Schmidt reactions on the corresponding cyclohex-2-enone. Further evidence for the mechanism of the Beckmann rearrangement of these unsaturated oximes is advanced. The central nervous system activity of the alkylated caprolactams is reported.

  介绍了以下六氢氮杂卓-2-酮（己内酰胺）的合成 在 C4 和 C6 上带有 1-4 个烷基或芳基的六氢氮杂卓-2-酮（己内酰胺）。 和 C6 上带有 1-4 个烷基或芳基的六氢氮杂卓-2-酮（己内酰胺）的合成。 环己-2-烯酮。关于这些不饱和环己-2-烯酮的贝克曼 这些不饱和肟的重排机理的进一步证据。中枢神经系统 报告了烷基化己内酰胺的中枢神经系统活性。
• Total Synthesis of (±)-Arohynapene B
  作者：Hideyuki Sugimura、Yuki Uchida

  DOI：10.1246/cl.2005.352

  日期：2005.3

  tetrahydronaphthalene ring was constructed by the Diels-Alder reaction between dimethyl acetylenedicarboxylate and the 1-(β-acetoxyvinyl)cyclohexene derivative, which was prepared from 3,5-dimethylcyclohexanone via the Ag + -catalyzed rearrangement of the propargylic acetate derivative. The introduction of the dienylcarboxylic acid side chain was accomplished by the Horner-Wadsworth-Emmons olefination repeatedly utilizing

  (')-arohynapene B 是一种从真菌菌株的发酵液中分离出来的抗球虫剂，已经实现了全合成。四氢萘环是通过乙炔二羧酸二甲酯和 1-(β-乙酰氧基乙烯基)环己烯衍生物之间的 Diels-Alder 反应构建的，1-(β-乙酰氧基乙烯基)环己烯衍生物是由 3,5-二甲基环己酮通过 Ag + 催化的炔乙酸衍生物重排制备的。二烯基羧酸侧链的引入是通过使用二乙基膦酰基乙酸乙酯反复进行Horner-Wadsworth-Emmons烯化来完成的。最后，小心去除保护基团导致 (')-aro-hynapene B。
• Method for the Production of Optically Active Carbonyl
  申请人：Jakel Christoph

  公开号：US20080269528A1

  公开（公告）日：2008-10-30

  The present invention relates to a process for preparing optically active carbonyl compounds by asymmetrically hydrogenating α,β-unsaturated carbonyl compounds in the presence of optically active transition metal catalysts which are soluble in the reaction mixture and have at least one carbon monoxide ligand. The present invention especially relates to a process for preparing optically active aldehydes or ketones, in particular citronellal, by asymmetrically hydrogenating the corresponding optically active α,β-unsaturated aldehydes or ketones.

  本发明涉及一种通过在存在可溶于反应混合物中并具有至少一个一氧化碳配体的光学活性过渡金属催化剂的情况下，对α，β-不饱和羰基化合物进行不对称氢化的方法。本发明特别涉及一种通过对相应的光学活性α，β-不饱和醛或酮进行不对称氢化而制备光学活性醛或酮的方法，特别是柠檬醛。

表征谱图