1-(2-羟基-环己基)-乙酮 | 33830-26-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 1-(2-羟基-环己基)-乙酮
• 英文名称: trans-1-acetyl-2-hydroxycyclohexane
• 英文别名: 1-(2-hydroxy-cyclohexyl)-ethanone；(+/-)-2-Acetyl-cyclohexanol；1-[(1S,2S)-2-hydroxycyclohexyl]ethanone
• CAS: 33830-26-1；63718-26-3；82150-13-8；127619-71-0；140630-67-7；140630-68-8
• 化学式: C₈H₁₄O₂
• 分子量: 142.198
• InChiKey: GPYOABAXMVHVBU-SFYZADRCSA-N

物化性质

• 沸点：
  242.3±33.0 °C(Predicted)
• 密度：
  1.055±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.88
• 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：

  (S)-(+)-alpha-甲氧基苯乙酸 、 1-(2-羟基-环己基)-乙酮 在 4-二甲氨基吡啶 、 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 生成
  参考文献：
  名称：

  Palladium-Catalyzed Asymmetric Silaborative C−C Cleavage of meso-Methylenecyclopropanes

  摘要：

  An enantioselective silaborative C-C cleavage of meso-methylenecyclopropanes (meso-MCPs) was achieved by using a palladium catalyst bearing a chiral monodentate phosphine ligand. The (R)-2-bis(3,5-dimethylphenyl)phosphino-1,1'-binaphthyl gave the highest enantioselectivity in the reactions with (methyldiphenylsilyl)pinacolborane at 50 degrees C, affording derivatives of 2-boryl-4-silyl-1-butene in high yields with high enantiomeric excesses. The reactions of bicyclic MCPs that have fused five- to eight-membered rings gave the corresponding products with 89-91% ee, whereas a little lower ee was observed in the reaction of a non-fused MCP (81% ee). Synthetic applications of the products were demonstrated through synthesis of beta-silyl ketones by H2O2 oxidation and synthesis of stereodefined homoallylic alcohols via homologation-allylboration sequence, in which the chiral beta-substituent of the allylborane has critical impact on the diastereochemical outcome.

  DOI：

  10.1021/ja0703170
• 作为产物：
  描述：

  2-(methyldiphenylsilyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 在 bis(dibenzylideneacetone)-palladium⁽⁰⁾ sodium hydroxide 、 双氧水 、 三氟乙酸 作用下， 以 甲醇 、 甲苯 为溶剂， 反应 65.0h， 生成 1-(2-羟基-环己基)-乙酮
  参考文献：
  名称：

  Palladium-Catalyzed Asymmetric Silaborative C−C Cleavage of meso-Methylenecyclopropanes

  摘要：

  An enantioselective silaborative C-C cleavage of meso-methylenecyclopropanes (meso-MCPs) was achieved by using a palladium catalyst bearing a chiral monodentate phosphine ligand. The (R)-2-bis(3,5-dimethylphenyl)phosphino-1,1'-binaphthyl gave the highest enantioselectivity in the reactions with (methyldiphenylsilyl)pinacolborane at 50 degrees C, affording derivatives of 2-boryl-4-silyl-1-butene in high yields with high enantiomeric excesses. The reactions of bicyclic MCPs that have fused five- to eight-membered rings gave the corresponding products with 89-91% ee, whereas a little lower ee was observed in the reaction of a non-fused MCP (81% ee). Synthetic applications of the products were demonstrated through synthesis of beta-silyl ketones by H2O2 oxidation and synthesis of stereodefined homoallylic alcohols via homologation-allylboration sequence, in which the chiral beta-substituent of the allylborane has critical impact on the diastereochemical outcome.

  DOI：

  10.1021/ja0703170

文献信息

• TBD-Catalyzed Direct 5- and 6-<i>enolexo</i>Aldolization of Ketoaldehydes
  作者：Cynthia Ghobril、Cyrille Sabot、Charles Mioskowski、Rachid Baati

  DOI：10.1002/ejoc.200800539

  日期：2008.8

  Treatment of unfunctionalized acyclic ketoaldehydes with a catalytic amount of 1,5,7-triazabicyclo[4.4.0]dec-5-ene induces a direct intramolecular 5- and 6-enolexo aldolization, furnishing 2-ketocyclopentanols and 2-ketocyclohexanols in good-to-excellent yields. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

  用催化量的 1,5,7-三氮杂双环 [4.4.0]dec-5-ene 处理未官能化的无环酮醛诱导直接的分子内 5-和 6-烯醇醛醇缩合，提供 2-酮环戊醇和 2-酮环己醇到优秀的产量。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
• Reductive Generation of Enolates from Enones Using Elemental Hydrogen:  Catalytic C−C Bond Formation under Hydrogenative Conditions
  作者：Hye-Young Jang、Ryan R. Huddleston、Michael J. Krische

  DOI：10.1021/ja021163l

  日期：2002.12.1

  the presence of a Rh(I) catalyst enables reductive enolate generation, as evidenced by electrophilic trapping of the enolate by appendant and exogenous aldehyde partners. The significance of these findings resides in the ability to regioselectivity generate and transform transition metal enolates under catalytic conditions that circumvent formation of stoichiometric byproducts.

  在 Rh(I) 催化剂的存在下，烯酮暴露于元素氢能够还原烯醇化物的生成，这可以通过附属物和外源性醛伙伴对烯醇化物的亲电捕获来证明。这些发现的重要性在于在催化条件下区域选择性生成和转化过渡金属烯醇化物的能力，从而避免了化学计量副产物的形成。
• Chiral orthoesters in organic synthesis: Novel reagents for the enantioselective acylation of silylenolethers
  作者：Luigi Longobardo、Giovanna Mobbili、Emilio Tagliavini、Claudio Trombini、Achille Umani-Ronchi

  DOI：10.1016/s0040-4020(01)90792-6

  日期：1992.1

  Dialkyl trans-2-alkoxy-2-alkyl-1,3-dioxolan-4,5-dicarboxylates and the corresponding N,N,N,N-tetramethyl-4,5-diamides have been prepared respectively from dialkyl tartrates or tartaric acid diamides. They smoothly reacted with silylenolethers in the presence of Lewis acids to give enantiomerically enriched (up to 90% d.e.) monoprotected 1,3-diketones. A dramatic dependence of the stereochemical outcome from the configuration of the enolic double bond of 4 has been observed. The products can be stereoselectively reduced to give configurationally defined monoprotected 3-ketols.
• Formation of β-hydroxyketones from α,β-epoxyketones by photoinduced single electron transfer reactions
  作者：J. Cossy、A. Bouzide、S. Ibhi、P. Aclinou

  DOI：10.1016/s0040-4020(01)81935-9

  日期：1991.9

  Irradiation of alpha,beta-epoxyketones in acetonitrile at 254 nm in the presence of triethylamine afforded beta-hydroxyketones in good to moderate yields.
• Titanocene-Promoted Intermolecular Couplings of Epoxides with Nitriles. An Easy Access to β-Hydroxyketones
  作者：A. Fernández-Mateos、S. Encinas Madrazo、P. Herrero Teijón、R. Rubio González

  DOI：10.1021/jo900479v

  日期：2009.5.15

  Radical couplings of epoxides and nitriles mediated by Cp2TiCl provide a diastereoselective route to the synthesis of beta-hydroxyketones. The conditions of this "aldol-like" reaction are mild enough to avoid the dehydration of the beta-hydroxyketone. The scope of the coupling reaction with functionalized and tetrasubstituted epoxides has been studied. The radical character of the coupling reactions is demonstrated.