4-氧代-6-苯基己酸甲酯 | 22187-89-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 酮酸及其衍生物
• 中文名称: 4-氧代-6-苯基己酸甲酯
• 英文名称: 4-oxo-6-phenylhexanoic acid methyl ester
• 英文别名: methyl 4-oxo-6-phenylhexanoate；4-oxo-6-phenyl-hexanoic acid methyl ester；4-Oxo-6-phenyl-hexansaeure-methylester；Methyl-4-keto-6-phenyl-hexanoat
• CAS: 22187-89-9
• 化学式: C₁₃H₁₆O₃
• 分子量: 220.268
• InChiKey: XJXBIMVJEMSRDD-UHFFFAOYSA-N

物化性质

• 沸点：
  187.5 °C(Press: 15 Torr)
• 密度：
  1.0869 g/cm3

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  16
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4-氧代-6-苯基己酸甲酯 在 [(-)-(R)-tetraMe-BITIOP]Ru(CF₃COO)2 盐酸 、 1-溴辛烷 、 氢气 作用下， 以 乙醇 为溶剂， 45.0 ℃ 、10.0 MPa 条件下， 反应 48.0h， 生成 (+)-(R)-5-(2-phenylethyl)dihydrofuran-2(3H)-one
  参考文献：
  名称：

  Process-scale preparation of enantiomerically pure γ-lactones by asymmetric hydrogenation of γ-ketoesters and comparative tests of the sensory properties of some antipodes

  摘要：

  A reliable methodology, applicable on a process-scale level, for producing enantiomerically pure chiral gamma-lactones by enantioselective hydrogenation of gamma-ketoesters, followed by cyclisation of the resulting gamma-hydroxyesters, has been developed. The multi-step procedure was transformed into a one-pot reaction. A very efficient chiral Ru-complex, based on the bilieteroaromatic diphosphine ligand tetraMe-BITIOP, was developed as a catalyst, capable of coupling fast kinetics with high stereoselection levels. Its structure was fully elucidated through P-31 NMR, EPR and X-ray single-crystal analyses. The optimal experimental conditions are as follows: hydrogen pressure = 30 psi, S/C ratio = 2000, 30% in weight substrate concentration. Yields are quantitative and enantiomeric excesses in the range 98-99.9%. Sensorial tests on the antipodes of two gamma-lactones demonstrated the very different properties of the enantiomers. (C) 2004 Published by Elsevier Ltd.

  DOI：

  10.1016/j.tetasy.2004.06.024
• 作为产物：
  描述：

  3-苯丙酸甲酯 在 偶氮二异丁腈 、 三正丁基氢锡 作用下， 以 二氯甲烷 、 甲苯 、 苯 为溶剂， 反应 1.75h， 生成 4-氧代-6-苯基己酸甲酯
  参考文献：
  名称：

  针对 crinipellin A 合成的新串联自由基环化

  摘要：

  我们描述了一种新的串联自由基环化策略，用于构建天然四喹烷 crinipellin A 的拥挤角三喹烷部分。 详细介绍了三个 5,5-二取代-1,4-二甲基-1,3-环戊二烯的制备和环化. 这种环化策略导致环戊二烯核的 1,4-官能化，由烯丙基环化介导。每次串联环化以 5:1 的比例产生两种非对映体三喹烷。次要的非对映异构体对 crinipellin A 的 D 环异丙基具有正确的相对立体化学。还描述了与自由基环化平行的串联阳离子环化

  DOI：

  10.1021/ja00181a033

文献信息

• NAD(P)⁺–NAD(P)H Models. 65. Photochemical Reductive Desulfonylation of β-Keto Sulfones with Hantzsch Ester
  作者：Masayuki Fujii、Kaoru Nakamura、Hideyuki Mekata、Shinzaburo Oka、Atsuyoshi Ohno

  DOI：10.1246/bcsj.61.495

  日期：1988.2

  A new procedure for the reductive desulfonylation of β-keto sulfones is described. The reaction proceeds under a photochemical conditions with the Hantzsch ester in pyridine in the presence of ruthenium(II). Various functional groups are unaffected under the reaction conditions. Application of the procedure to the syntheses of certain natural products is also described.

  描述了一种用于 β-酮砜还原脱磺酰化的新程序。在钌 (II) 存在下，该反应在光化学条件下与在吡啶中的 Hantzsch 酯进行。各种官能团在反应条件下不受影响。还描述了该程序在某些天然产物合成中的应用。
• DESULFONYLATION OF β-KETO SULFONES WITH THE HANTZSCH ESTER, AN NAD(P)H MODEL
  作者：Kaoru Nakamura、Masayuki Fujii、Hideyuki Mekata、Shinzaburo Oka、Atsuyoshi Ohno

  DOI：10.1246/cl.1986.87

  日期：1986.1.5

  Carbon–sulfur bonds in β-keto sulfones were reduced smoothly to carbon–hydrogen bonds with the Hantzsch ester, a model of NAD(P)H.

  β-酮砜中的碳 - 硫键与 Hantzsch 酯（NAD（P）H 的模型）平滑地还原为碳 - 氢键。
• Direct Intermolecular Hydroacylation of <i>N</i>,<i>N</i>-Dialkylacrylamides with Aldehydes Catalyzed by a Cationic Rhodium(I)/dppb Complex
  作者：Ken Tanaka、Yu Shibata、Takeshi Suda、Yuji Hagiwara、Masao Hirano

  DOI：10.1021/ol070153s

  日期：2007.3.1

  [structure: see text]. A cationic rhodium(I)/dppb complex catalyzed direct intermolecular hydroacylation of N,N-dialkylacrylamides with both aliphatic and aromatic aldehydes has been achieved through the stabilization of acylrhodium intermediates by alkene chelation to rhodium. This method represents a versatile new route to gamma-ketoamides in view of the high atom economy and commercial availability

  [结构：见文字]。阳离子铑（I）/ dppb络合物通过将烯烃与铑螯合来稳定酰基铑中间体，从而实现了N，N-二烷基丙烯酰胺与脂肪族和芳香族醛的直接分子间加氢酰化反应。考虑到高原子经济性和底物的商业可用性，该方法代表了一种通用的制备γ-酮酰胺的新途径。
• Cross metathesis of allyl alcohols: how to suppress and how to promote double bond isomerization
  作者：Bernd Schmidt、Sylvia Hauke

  DOI：10.1039/c3ob40167g

  日期：——

  formation of ketones, resulting from uncontrolled and undesired double bond isomerization. By conducting the CM in the presence of phenol, the catalyst loading and the reaction time required for quantiative conversion can be reduced, and isomerization can be suppressed. On the other hand, consecutive isomerization can be deliberately promoted by evaporating excess methyl acrylate after completing cross

  在标准条件下，烯丙醇和 丙烯酸甲酯伴随着由于不受控制和不希望的双键异构化导致的酮的形成。通过在以下人员在场的情况下执行CM苯酚，可以减少定量转化所需的催化剂载量和反应时间，并且可以抑制异构化。另一方面，通过过量蒸发可以有意地促进连续的异构化。丙烯酸甲酯 完成交叉复分解后，并添加碱或硅烷作为化学触发剂。
• Diastereo- and Enantioselective Construction of 6,7-Dioxabicyclo[2.2.1]heptane Derivatives by a Dirhodium(II)-Catalyzed Intramolecular C–H Insertion Reaction
  作者：Masahiro Anada、Shunichi Hashimoto、Taku Miyazawa、Kozue Imai、Motoki Ito、Koji Takeda、Shigeki Matsunaga

  DOI：10.3987/com-16-s(s)72

  日期：——

  The first diastereo- and enantioselective construction of bridged bicyclic ring systems by an intramolecular C-H insertion reaction is described. With dirhodium(II) tetrakis[N-phthaloyl-(S)-tert-leucinate], Rh2(S-PTTL)4, the C-H insertion of alpha-alkyl-alpha-diazoesters containing an ethylene ketal moiety at the gamma-position provided methyl 6,7-dioxabicyclo[2.2.1]heptane-3-carboxylate derivatives with up to 95% ee and perfect diastereoselectivity.