cis-2,3-dimethylcyclohexanone | 167073-61-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: cis-2,3-dimethylcyclohexanone
• 英文别名: cis-2,3-Dimethyl-cyclohexanon；Cyclohexanone, 2,3-dimethyl-, (2R,3R)-；(2R,3R)-2,3-dimethylcyclohexan-1-one
• CAS: 167073-61-2
• 化学式: C₈H₁₄O
• 分子量: 126.199
• InChiKey: OZCVOEUWYVVVME-RNFRBKRXSA-N

物化性质

• 沸点：
  176.8±8.0 °C(Predicted)
• 密度：
  0.882±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 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：

  cis-2,3-dimethylcyclohexanone 、 sodium methylate 生成 (2R,3S)-2,3-dimethylcyclohexan-1-one
  参考文献：
  名称：

  WOOD, S. E.;RICKBORN, B., J. ORG. CHEM., 1983, 48, N 4, 555-562

  摘要：

  DOI：
• 作为产物：
  描述：

  trans-2,3-Dimethyl-cyclohexanol 生成 cis-2,3-dimethylcyclohexanone
  参考文献：
  名称：

  WOOD, S. E.;RICKBORN, B., J. ORG. CHEM., 1983, 48, N 4, 555-562

  摘要：

  DOI：

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。
• Total Synthesis and Structure Revision of Halioxepine
  作者：Caroline Poock、Markus Kalesse

  DOI：10.1002/chem.202004847

  日期：2021.1.21

  total synthesis of halioxepine is accomplished using a 1,4‐addition for constructing the quaternary center at C10 and a halo etherification for the generation of the tertiary ether at C7. The correct structure of halioxepine was determined by assembling different enantiomeric building blocks and by changing the relative configuration between C10 and C15.

  卤氧杂环己烷的首次全合成是通过 1,4 加成在 C10 处构建四级中心和卤代醚化在 C7 处生成叔醚来完成的。通过组装不同的对映体结构单元并改变 C10 和 C15 之间的相对构型，确定了卤氧杂平的正确结构。
• COMPOUND
  申请人：Woo Lok Wai Lawrence

  公开号：US20120238550A1

  公开（公告）日：2012-09-20

  There is provided a compound of formula I wherein Z is selected from N and CR 22 , wherein R 22 is H or a bond with D; wherein D is selected from a bond, C═O, and linear or branched hydrocarbon groups having a carbon chain of from 1 to 6 carbon atoms, wherein the carbon chain optionally contains an oxy group (═O), an ether (—O—) or thioether (—S—) link, wherein R 1 is selected from: triazolyl, imidazolyl, pyrimidinyl radical wherein each of R 2 to R 6 is independently selected from —H, NO 2 , halo, —CN, —N[(C═O) 0-1 R 12 ][(C═O) 0-1 R 13 ] and —(CH 2 ) 0-1 R 14 , or two adjacent groups of R 2 to R 6 , together with the carbon atoms to which they are attached, form a ring, wherein at least one of R 2 to R 6 is —CN, wherein (i) at least one of R 2 to R 6 is —(CH 2 ) 0-1 R 14 , or (ii) at least one of R 2 to R 6 is —N[(C═O) 0-1 R 12 ][(C═O) 0-1 R 13 ], or (iii) at least two adjacent groups of R 2 to R 6 together with the carbon atoms to which they are attached, form a ring, or (iv) at least one of R 2 to R 6 is —(CH 2 ) 0-1 —O—R′ 14 , wherein R 12 and R 13 are independently selected from H, linear or branched hydrocarbon groups having a carbon chain of from 1 to 10 carbon atoms, or together with the atoms to which they are attached, may form a mono or bicyclic ring having from 5 to 14 ring members wherein R 14 is selected from: aliphatic ring systems unsubstituted or substituted monocyclic aliphatic heterocycles; unsubstituted or substituted heteroaryl radical, and unsubstituted or substituted phenyl group; the group of formula wherein t is 1 or 2 wherein R′ 14 is a unsubstituted or substituted phenyl group; wherein each of R 7 to R 11 is independently selected from —H, NO 2 , halo, —O—(C 1 -C 6 )haloalkyl, (C 1 -C 6 )haloalkyl, (C 1 -C 6 )alkyl, —CN, —OH, —OPh, —OBn, -Ph, —OSO 2 NR 15 R 16 , —SO 2 R 26 , —SO 2 NR 27 R 28 , —O—(C 1 -C 6 )alkyl, —(C═O) 0-1 NR 29 R 30 and —CO(O) 0-1 R 31 ; wherein R 15 and R 16 are independently selected from H, alkyl, cycloalkyl, alkenyl, acyl and aryl, or combinations thereof, or together represent alkylene, wherein the or each alkyl or cycloalkyl or alkenyl optionally contain one or more hetero atoms or groups wherein each of R 26 to R 31 is independently selected from H, alkyl, cycloalkyl, alkenyl, acyl and aryl, or combinations thereof, or together represent alkylene, wherein the or each alkyl or cycloalkyl or alkenyl optionally contain one or more hetero atoms or groups; or any pharmaceutically acceptable salts thereof.

  提供了一种化合物，其化学式为I，其中Z从N和CR22中选择，其中R22为H或与D形成键结；D从键，C═O和线性或支链碳链为1至6个碳原子的烃基中选择，其中碳链可以包含氧基（═O），醚（—O—）或硫醚（—S—）连接，其中R1从三唑基，咪唑基，嘧啶基中选择；R2至R6中的每个独立地选择自—H，NO2，卤素，—CN，—N[(C═O)0-1R12][(C═O)0-1R13]和—(CH2)0-1R14，或R2至R6中的两个相邻基团连同它们附着的碳原子形成环；其中至少一个R2至R6为—CN；其中（i）至少一个R2至R6为—(CH2)0-1R14，或（ii）至少一个R2至R6为—N[(C═O)0-1R12][(C═O)0-1R13]，或（iii）至少两个相邻的R2至R6基团连同它们附着的碳原子形成环，或（iv）至少一个R2至R6为—(CH2)0-1—O—R′14，其中R12和R13独立选择自1至10个碳原子的线性或支链烃基，或与它们附着的原子一起形成具有从5至14个环成员的单环或双环；其中R14从：脂环系统，未取代或取代的单环脂肪族杂环，未取代或取代的杂芳基基团和未取代或取代的苯基中选择；式中t为1或2；其中R′14为未取代或取代的苯基；其中R7至R11中的每个独立地选择自—H，NO2，卤素，—O—（C1-C6）卤代烷基，（C1-C6）卤代烷基，（C1-C6）烷基，—CN，—OH，—OPh，—OBn，-Ph，—OSO2NR15R16，—SO2R26，—SO2NR27R28，—O—（C1-C6）烷基，—（C═O）0-1NR29R30和—CO（O）0-1R31；其中R15和R16独立选择自H，烷基，环烷基，烯基，酰基和芳基，或它们的组合，或一起表示为烷基，其中每个烷基或环烷基或烯基可以选择包含一个或多个杂原子或基团；其中R26至R31中的每个独立地选择自H，烷基，环烷基，烯基，酰基和芳基，或它们的组合，或一起表示为烷基，其中每个烷基或环烷基或烯基可以选择包含一个或多个杂原子或基团；或其任何药学上可接受的盐。
• 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。
• Regioselective Oxidation of Nonactivated Alkyl C–H Groups Using Highly Structured Non-Heme Iron Catalysts
  作者：Laura Gómez、Mercè Canta、David Font、Irene Prat、Xavi Ribas、Miquel Costas

  DOI：10.1021/jo302196q

  日期：2013.2.15

  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).