(3S,4R)-3,4-dimethylcyclohexanone | 75364-88-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (3S,4R)-3,4-dimethylcyclohexanone
• 英文别名: cis-3,4-dimethylcyclohexanone；cis-3,4-Dimethyl-cyclohexanon；(3S,4R)-3,4-dimethylcyclohexan-1-one
• CAS: 75364-88-4
• 化学式: C₈H₁₄O
• 分子量: 126.199
• InChiKey: ZDCYWXYPRPCJOY-RQJHMYQMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 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：

  (3S,4R)-3,4-dimethylcyclohexanone 、 溶剂黄146 在 碘苯二乙酸 、 三氟化硼乙醚 作用下， 反应 3.0h， 以40.5%的产率得到
  参考文献：
  名称：

  合成高非对映选择性的α-酰氧化环酮类化合物的方法

  摘要：

  本申请属于合成化学技术领域，具体涉及合成高非对映选择性的α‑酰氧化环酮类化合物的方法。本发明所提供的合成方法包括：在高价碘试剂的氧化催化作用下，环酮类化合物、路易斯酸和酰氧化试剂在反应溶剂中进行反应。该方法反应条件温和可控、操作简单优化，产物单一，非对映选择性高，适用于多种环酮类化合物。与现有技术相比，本发明的优点在于，通过上述方法制备得到的产物，其非对映异构体选择性高达12：1，适用于实验室和工厂制备特定立体构型的α‑酰氧化环酮类药物中间体和精细化学品。

  公开号：

  CN108358780B
• 作为产物：
  描述：

  cis-1,2-dimethylcyclohexane 在 Δ-[Fe(CF3SO3)2((R,R,R)-MCPP)] 、 双氧水 、 溶剂黄146 作用下， 以 乙腈 为溶剂， 生成 cis-1,2-dimethylcyclohexanol 、 cis-2,3-dimethylcyclohexanone 、 (3S,4R)-3,4-dimethylcyclohexanone
  参考文献：
  名称：

  Regioselective Oxidation of Nonactivated Alkyl C–H Groups Using Highly Structured Non-Heme Iron Catalysts

  摘要：

  Selective oxidation of alkyl C-H groups constitutes one of the highest challenges in organic synthesis. In this work, we show that mononuclear iron coordination complexes Lambda-[Fe(CF3SO3)(2)((S,S,R)-MCPP)] (Lambda-1P), Delta-[Fe(CF3SO3)(2)((R,R,R)-MCPP)] (Delta-1P), Lambda-[Fe(CF3SO3)(2)((S,S,R)-BPBPP)] (Lambda-2P), and Delta-[Fe(CF3SO3)(2)((R,R,R)-BPBPP)] (Delta-2P) catalyze the fast, efficient, and selective oxidation of nonactivated alkyl C-H groups employing H2O2 as terminal oxidant. These complexes are based on tetradentate N-based ligands and contain iron centers embedded in highly structured coordination sites defined by two bulky 4,5-pinenopyridine donor ligands, a chiral diamine ligand backbone, and chirality at the metal (Lambda or Delta). X-ray diffraction analysis shows that in Lambda-1P and Lambda-2P the pinene rings create cavity-like structures that isolate the iron site. The efficiency and regioselectivity in catalytic C-H oxidation reactions of these structurally rich complexes has been compared with those of Lambda-[Fe(CF3SO3)(2)((S,S)-MCP)] (Lambda-1), Lambda-[Fe(CF3SO3)(2)((S,S)-BPBP)] (Lambda-2), Delta-[Fe(CF3SO3)(2)((R,R)-BPBP)] (Delta-2), Lambda-[Fe(CH3CN)(2)((S,S)-BPBP)] (SbF6)(2) (Lambda-2SbF(6)), and Delta-[Fe(CH3CN)(2)((R,R)-BPBP)](SbF6)(2) (Delta-2SbF(6)), which lack the steric bulk introduced by the pinene rings. Cavity-containing complexes Lambda-1P and Lambda-2P exhibit enhanced activity in comparison with Delta-1P, Delta-2P, Lambda-1, Lambda-2, and Lambda-2SbF(6). The regioselectivity exhibited by catalysts Lambda-1P, Lambda-2P, Delta-1P, and Delta-2P in the C-H oxidation of simple organic molecules can be predicted on the basis of the innate properties of the distinct C-H groups of the substrate. However, in specific complex organic molecules where oxidation of multiple C-H sites is competitive, the highly elaborate structure of the catalysts allows modulation of C-H regioselectivity between the oxidation of tertiary and secondary C-H groups and also among multiple methylene sites, providing oxidation products in synthetically valuable yields. These selectivities complement those accomplished with structurally simpler oxidants, including non-heme iron catalysts Lambda-2 and Lambda-2SbF(6).

  DOI：

  10.1021/jo302196q

文献信息

• C–H Oxidation by H₂O₂ and O₂ Catalyzed by a Non-Heme Iron Complex with a Sterically Encumbered Tetradentate N-Donor Ligand
  作者：Qiao Zhang、John D. Gorden、Christian R. Goldsmith

  DOI：10.1021/ic402501k

  日期：2013.12.2

  substrates, the neopentyl groups destabilize the metal-based oxidants generated from H2O2 and the Fe(II) complex. The presence of benzylic substrates with weak C–H bonds stabilizes an intermediate which we have tentatively assigned as a high-spin ferric hydroperoxide species. The oxidant generated from O2 reacts with allylic and benzylic C–H bonds in the absence of a sacrificial reductant; less substrate

  的化合物Ñ，N' -dineopentyl- Ñ，Ñ ' -双（2-吡啶基甲基）-1,2-乙二胺（dnbpn）及其亚铁复杂的[Fe（dnbpn）（OTF）2 ]合成的。Fe（II）络合物用于催化H 2 O 2和O 2氧化烃。尽管H 2 O 2催化了烷烃的氧化与大多数先前报道的非血红素铁催化剂相关的那些相比，对叔碳显示出对仲碳而不是叔碳的更高的偏好，催化活性显着降低。除了将催化的氧化导向底物的较少拥挤的C–H键外，新戊基还使由H 2 O 2和Fe（II）络合物生成的金属基氧化剂不稳定。具有弱C–H键的苄基底物的存在稳定了一种中间体，我们暂时将其定为高纺氢过氧化铁物种。由O 2产生的氧化剂在不存在牺牲性还原剂的情况下与烯丙基和苄基CH键反应；与使用O 2作为末端氧化剂的相关先前描述的系统相比，观察到的底物脱氢更少。
• Hydrogen-atom and oxygen-atom transfer reactivities of iron(<scp>iv</scp>)-oxo complexes of quinoline-substituted pentadentate ligands
  作者：Sandip Munshi、Arup Sinha、Solomon Yiga、Sridhar Banerjee、Reena Singh、Md. Kamal Hossain、Matti Haukka、Andrei Felipe Valiati、Ricardo Dagnoni Huelsmann、Edmar Martendal、Rosely Peralta、Fernando Xavier、Ola F. Wendt、Tapan K. Paine、Ebbe Nordlander

  DOI：10.1039/d1dt03381f

  日期：——

  ated complex is in a mixed spin state. The steric bulk of the quinoline moieties forces the axial ligands to deviate from the Fe–Naxial axis. A higher deviation/tilt is noted for the high spin complexes, while the acetonitrile coordinated complex displays least deviation. This deviation from linearity is slightly less in the analogous low-spin iron(II) complex [FeII(L1-Qn)(NCMe)]2+ of the related asymmetric

  一系列具有通式 [Fe II ( L2-Qn )(L)] n + ( n = 1, L = F - , Cl - ; n = 2, L = NCMe, H 2 O的铁( II )配合物) 已被分离和表征。X 射线晶体学数据表明，金属-配体键距随第六配体的不同配体场强而变化。以氟化物、氯化物和水为轴向配体的配合物是高自旋的，而乙腈配位的配合物则处于混合自旋状态。喹啉部分的空间体积迫使轴向配体偏离 Fe-N轴向轴。高自旋配合物的偏差/倾斜度较高，而乙腈配位配合物的偏差最小。由于仅存在一种空间要求高的喹啉，因此在相关不对称配体L1-Qn的类似低自旋铁 ( II ) 配合物 [Fe II ( L1-Qn )(NCMe)] 2+中，这种与线性的偏差略小部分。两种铁( II )-乙腈配合物[Fe II ( L2-Qn )(NCMe)] 2+和[Fe II ( L1-Qn )(NCMe)] 2+生成相应的铁(
• NOVEL SPIRO IMIDAZOLONES AS GLUCAGON RECEPTOR ANTAGONISTS, COMPOSITIONS, AND METHODS FOR THEIR USE
  申请人：Wong Michael K.

  公开号：US20130012434A1

  公开（公告）日：2013-01-10

  The present invention relates to compounds of the general formula: wherein ring A, ring B, R1, R3, Z, L1, and L2 are selected independently of each other and are as defined herein, to compositions comprising the compounds, and to methods of using the compounds as glucagon receptor antagonists and for the treatment or prevention of type 2 diabetes and conditions related thereto.

  本发明涉及通式化合物：其中环A、环B、R1、R3、Z、L1和L2是彼此独立选择并如下所定义的，以及包含该化合物的组合物，以及使用该化合物作为胰高血糖素受体拮抗剂以及治疗或预防2型糖尿病及相关疾病的方法。
• CATALYST-CONTROLLED ALIPHATIC C-H OXIDATIONS
  申请人：THE BOARD OF TRUSTEES OF THE UNIVERSITY OF ILLINOIS

  公开号：US20160214097A1

  公开（公告）日：2016-07-28

  The invention provides simple small molecule, non-heme iron catalyst systems with broad substrate scope that can predictably enhance or overturn a Substrate Control Catalyst Control substrate's inherent reactivity preference for sp3-hybridized C—H bond oxidation. The invention also provides methods for selective aliphatic C—H bond oxidation. Furthermore, a structure-based catalyst reactivity model is disclosed that quantitatively correlates the innate physical properties of the substrate to the site-selectivities observed as a function of the catalyst. The catalyst systems can be used in combination with oxidants such as hydrogen peroxide to effect highly selective oxidations of unactivated sp3 C—H bonds over a broad range of substrates.

  本发明提供了简单的小分子、非血红素铁催化剂系统，具有广泛的底物范围，可以可预测地增强或颠覆基质控制催化剂控制底物对sp3杂化C-H键氧化的固有反应性偏好。本发明还提供了选择性脂肪族C-H键氧化的方法。此外，还公开了一种基于结构的催化剂反应性模型，该模型定量地将底物的固有物理性质与作为催化剂函数的位点选择性相互关联。这些催化剂系统可以与过氧化氢等氧化剂结合使用，对广泛的底物进行高度选择性的未活化的sp3 C-H键氧化。
• US8361959B2
  申请人：——

  公开号：US8361959B2

  公开（公告）日：2013-01-29

表征谱图