cis-1-((1R,2S)-2-hydroxycyclohexyl)ethan-1-one | 935697-24-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: cis-1-((1R,2S)-2-hydroxycyclohexyl)ethan-1-one
• 英文别名: cis-1-(2-hydroxycyclohexyl)ethanone；1-[(1R,2S)-2-hydroxycyclohexyl]ethanone
• CAS: 935697-24-8
• 化学式: C₈H₁₄O₂
• 分子量: 142.198
• InChiKey: GPYOABAXMVHVBU-YUMQZZPRSA-N

物化性质

• 沸点：
  242.3±33.0 °C(Predicted)
• 密度：
  1.055±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(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 cis-1-((1R,2S)-2-hydroxycyclohexyl)ethan-1-one
  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

• Cytochrome P450 Catalyzed Oxidative Hydroxylation of Achiral Organic Compounds with Simultaneous Creation of Two Chirality Centers in a Single CH Activation Step
  作者：Gheorghe-Doru Roiban、Rubén Agudo、Manfred T. Reetz

  DOI：10.1002/anie.201310892

  日期：2014.8.11

  enantioselectivity is ensured. The present study demonstrates that such control is possible by using wild type or mutant forms of the monooxygenase cytochrome P450 BM3 as catalysts in the oxidative hydroxylation of methylcyclohexane and seven other monosubstituted cyclohexane derivatives.

  由合成试剂，催化剂或酶介导的非手性或手性有机化合物的区域和立体选择性氧化羟基化反应通常会导致在相应的对映异构或非对映异构醇中出现一个新的手性中心的形成。相比之下，当使适当的非手性化合物受到这种CH活化作用时，可以同时创建两个具有定义的相对和绝对构型的手性中心，但前提是要确保对区域，非对映和对映选择性的控制。本研究表明，通过使用野生型或突变形式的单加氧酶细胞色素P450 BM3作为甲基环己烷和其他七个单取代环己烷衍生物的氧化羟化反应的催化剂，这种控制是可能的。
• 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.
• MOLANDER, G. A.;HAHN, G., J. ORG. CHEM., 1986, 51, N 13, 2596-2599
  作者：MOLANDER, G. A.、HAHN, G.

  DOI：——

  日期：——
• Palladium-Catalyzed Asymmetric Silaborative C−C Cleavage of <i>meso</i>-Methylenecyclopropanes
  作者：Toshimichi Ohmura、Hiroki Taniguchi、Yoshiyuki Kondo、Michinori Suginome

  DOI：10.1021/ja0703170

  日期：2007.3.1

  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.