[(1S,2R,5R)-2-(2-hydroxypropan-2-yl)-5-methylcyclohexyl] 2,2-dimethylpropanoate | 1421312-59-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: [(1S,2R,5R)-2-(2-hydroxypropan-2-yl)-5-methylcyclohexyl] 2,2-dimethylpropanoate
• CAS: 1421312-59-5
• 化学式: C₁₅H₂₈O₃
• 分子量: 256.386
• InChiKey: YRYIOBJBGPZGQG-UTUOFQBUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.15
• 重原子数：
  18.0
• 可旋转键数：
  2.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  46.53
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为产物：
  描述：

  (+)-neomenthyl pivalate 在 [Fe(CF₃SO₃)₂((S,S)-N,N’-bis(2-pyridylmethyl)-2,2’-bipyrrolidine)] 、 双氧水 、 溶剂黄146 作用下， 以 水 、 乙腈 为溶剂， 反应 0.17h， 生成 [(1S,2R,5R)-2-(2-hydroxypropan-2-yl)-5-methylcyclohexyl] 2,2-dimethylpropanoate 、 [(1S,2S,5S)-5-methyl-4-oxo-2-propan-2-ylcyclohexyl] 2,2-dimethylpropanoate
  参考文献：
  名称：

  易于接触的大铁催化剂在甾类底物的氧化中表现出位选择性

  摘要：

  描述了大铁络合物在温和条件下用过氧化氢催化烷基CH键的位点选择性氧化。通过在三齿氨基吡啶配体中吡啶的间位连接三烷基甲硅烷基，可以在铁中心引入大分子的立体化，这种作用转化为高产物产量，增强了仲碳氢键与仲碳氢键的优先氧化作用，并具有更高的分离能力。对萜类化合物和甾体基质中的亚甲基位点进行位点选择性氧化。甾族底物中C6和C12亚甲基位的空位选择性氧化显示出受催化剂手性支配。

  DOI：

  10.1002/anie.201600785

文献信息

• 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).