(+)-(2R,5S)-2-(1-hydroxy-1-methylethyl)-5-methylcyclohexanone | 57129-10-9

• 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: (+)-(2R,5S)-2-(1-hydroxy-1-methylethyl)-5-methylcyclohexanone
• 英文别名: 8-Hydroxymenthone；(2R,5S)-2-(2-hydroxypropan-2-yl)-5-methylcyclohexan-1-one
• CAS: 57129-10-9
• 化学式: C₁₀H₁₈O₂
• 分子量: 170.252
• InChiKey: QNZZGEDTDYWNFN-YUMQZZPRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (+)-(2R,5S)-2-(1-hydroxy-1-methylethyl)-5-methylcyclohexanone 在 4-二甲氨基吡啶 、 盐酸羟胺 作用下， 以 甲醇 为溶剂， 反应 24.0h， 以96%的产率得到(+)-(2R,5S)-2-(1-hydroxy-1-methylethyl)-5-methylcyclohexanone oxime
  参考文献：
  名称：

  Chiral dioxomolybdenum(VI) complexes for enantioselective alkene epoxidation

  摘要：

  Chiral dioxomolybdenum(M) complexes of the type MoO2Cl2(L*) (L* = oxime), MoO2(THF)(2)L* (L* = cis-p-menthane-3,8-diol) and MoO2Cl(THF)L* (L* = 8-phenylthioneomenthol and 8-phenylthioisoneomenthol) have been prepared in good yields by reacting MoO2Cl2(THF)(2) with the appropriate chiral organic bidentate O,O-, O,N- and O,S-ligands. The complexes were characterised by solution NMR (H-1, C-13, Mo-95) and IR spectroscopy as well as elementary analysis, and were evaluated as catalysts in solution for the asymmetric epoxidation of cis-beta -methylstyrene by tert-butylhydroperoxide (TBHP). The cis-diol complex shows high catalytic activity and enantiomeric excesses of up to 25%. An attempt was made to immobilise the complex MoO2(THF)Cl[(-)-8-phenylthioneomenthol] within the channels of MCM-41 mesoporous silica by using a tethering ligand [L = NC(CH2)(3)Si(OEt)(3)]. The material was characterised by powder X-ray diffraction (XRD), IR spectroscopy and magic-angle-spinning (MAS) NMR (C-13, Si-29). Catalytic examinations demonstrated that it was active in the epoxidation of cyclooctene by TBHP. (C) 2001 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0022-328x(00)00790-7
• 作为产物：
  描述：

  (1S,3R,4S)-p-menthane-3,8-diol 在 吡啶 、 chromium(VI) oxide 作用下， 以 二氯甲烷 为溶剂， 反应 0.75h， 以89%的产率得到(+)-(2R,5S)-2-(1-hydroxy-1-methylethyl)-5-methylcyclohexanone
  参考文献：
  名称：

  Chiral dioxomolybdenum(VI) complexes for enantioselective alkene epoxidation

  摘要：

  Chiral dioxomolybdenum(M) complexes of the type MoO2Cl2(L*) (L* = oxime), MoO2(THF)(2)L* (L* = cis-p-menthane-3,8-diol) and MoO2Cl(THF)L* (L* = 8-phenylthioneomenthol and 8-phenylthioisoneomenthol) have been prepared in good yields by reacting MoO2Cl2(THF)(2) with the appropriate chiral organic bidentate O,O-, O,N- and O,S-ligands. The complexes were characterised by solution NMR (H-1, C-13, Mo-95) and IR spectroscopy as well as elementary analysis, and were evaluated as catalysts in solution for the asymmetric epoxidation of cis-beta -methylstyrene by tert-butylhydroperoxide (TBHP). The cis-diol complex shows high catalytic activity and enantiomeric excesses of up to 25%. An attempt was made to immobilise the complex MoO2(THF)Cl[(-)-8-phenylthioneomenthol] within the channels of MCM-41 mesoporous silica by using a tethering ligand [L = NC(CH2)(3)Si(OEt)(3)]. The material was characterised by powder X-ray diffraction (XRD), IR spectroscopy and magic-angle-spinning (MAS) NMR (C-13, Si-29). Catalytic examinations demonstrated that it was active in the epoxidation of cyclooctene by TBHP. (C) 2001 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0022-328x(00)00790-7

文献信息

• Studies on olefin epoxidation with t-BuOOH catalysed by dioxomolybdenum(VI) complexes of a novel chiral pyridyl alcoholate ligand
  作者：Anabela A. Valente、Isabel S. Gonçalves、Andre´ D. Lopes、Jose´ E. Rodríguez-Borges、Martyn Pillinger、Carlos C. Romão、João Rocha、Xerardo García-Mera

  DOI：10.1039/b102523f

  日期：——

  The chiral dioxomolybdenum(VI) complexes [MoCl(1R,2S,5S)-8-trimethylsilyloxy-1-(2-pyridyl)mentholato}(O)2(THF)] and [Mo(1R,2S,5S)-8-trimethylsilyloxy-1-(2-pyridyl)mentholato}2(O)2] have been prepared in good yields by reaction of the solvent substituted complex [MoCl2O2(THF)2] with one or two equivalents of chiral 2′-pyridyl alcohol. The optically active aminoalcohol was obtained by reaction of 2-pyridyllithium with (−)-(2S,5S)-8-trimethylsilyloxymenthone. The complexes are active catalysts in the homogeneous epoxidation of cyclic and linear olefins, dienes and terpenes by t-BuOOH. They present remarkable activity and excellent product selectivity in cyclooctene epoxidation (cyclooctene oxide was obtained in quantitative yield). In the case of limonene, regioselectivity is high in favour of the epoxidation of the internal cyclic double bond. Ring opening activity was also observed for α-pinene oxide, producing campholenic aldehyde and epoxy campholenic aldehyde.

  手性二氧钼(VI)配合物[MoCl(1R,2S,5S)-8-三甲基硅氧基-1-(2-吡啶基)薄荷醇配体}(O)2(THF)]和[Mo(1R,2S,5S)-8-三甲基硅氧基-1-(2-吡啶基)薄荷醇配体}2(O)2]通过溶剂取代的配合物[MoCl2O2(THF)2]与一个或两个当量的手性2′-吡啶醇反应制备得到，产率良好。通过2-吡啶基锂与(−)-(2S,5S)-8-三甲基硅氧基薄荷酮的反应得到光学活性氨基醇。这些配合物作为t-BuOOH存在下环状和直链烯烃、二烯和萜烯的均相环氧化反应的活性催化剂。它们在环辛烯环氧化反应中表现出显著的活性和优异的产品选择性（环辛烯氧化物以定量产率获得）。在柠檬烯的情况下，区域选择性较高，有利于内部环双键的环氧化。还观察到α-蒎烯氧化物的开环活性，生成蒎烯醛和环氧蒎烯醛。