(-)-(5S)-3-ethyl-4,4-dimethyl-5-hydroxycyclohex-2-enone | 681029-62-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (-)-(5S)-3-ethyl-4,4-dimethyl-5-hydroxycyclohex-2-enone
• 英文别名: (5S)-3-ethyl-5-hydroxy-4,4-dimethylcyclohex-2-en-1-one
• CAS: 681029-62-9
• 化学式: C₁₀H₁₆O₂
• 分子量: 168.236
• InChiKey: QFYBXJIALUKAGM-VIFPVBQESA-N

物化性质

• 沸点：
  273.4±39.0 °C(Predicted)
• 密度：
  1.006±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 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：

  (-)-(5S)-3-ethyl-4,4-dimethyl-5-hydroxycyclohex-2-enone 在 咪唑 、 ruthenium trichloride 、 sodium periodate 作用下， 以 四氯化碳 、 水 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 73.0h， 生成 (S)-3-((tert-butyldimethylsilyl)oxy)-4,4-dimethyl-5-oxoheptanoic acid
  参考文献：
  名称：

  Asymmetric aldol reactions using catalytic d(+)-proline: a new, economic and practical approach to a commonly employed C1–C6 keto-acid synthon of the epothilones

  摘要：

  A new approach to ketoacid 4, a common C1-C6 fragment used in the total synthesis of epothilones was initiated by direct aldol reaction of acetone with a pivaldehyde-like substance 5, catalyzed with D-proline, leading to a 2,6-diketoalcohol with better than 99% ee. Further intramolecular closure of the diketone 8 followed by oxidation of the silyl protected hydroxycyclohexenone 14 led to the desired product 4. None of the steps have been optimized, yet the overall yield for the four-step process is 31%. The use of commercially available D-proline to construct the chiral center of 4 under very mild reaction conditions provided an economical and practical method for its construction. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2003.12.048
• 作为产物：
  描述：

  (-)-(4S)-4-hydroxy-5,5-dimethyl-2,6-octanedione 在 四氢吡咯 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以76%的产率得到(-)-(5S)-3-ethyl-4,4-dimethyl-5-hydroxycyclohex-2-enone
  参考文献：
  名称：

  Asymmetric aldol reactions using catalytic d(+)-proline: a new, economic and practical approach to a commonly employed C1–C6 keto-acid synthon of the epothilones

  摘要：

  A new approach to ketoacid 4, a common C1-C6 fragment used in the total synthesis of epothilones was initiated by direct aldol reaction of acetone with a pivaldehyde-like substance 5, catalyzed with D-proline, leading to a 2,6-diketoalcohol with better than 99% ee. Further intramolecular closure of the diketone 8 followed by oxidation of the silyl protected hydroxycyclohexenone 14 led to the desired product 4. None of the steps have been optimized, yet the overall yield for the four-step process is 31%. The use of commercially available D-proline to construct the chiral center of 4 under very mild reaction conditions provided an economical and practical method for its construction. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2003.12.048

文献信息

• [EN] SYNTHESIS OF THE C1-C6 KETO-ACID SYNTHON OF THE EPOTHILONES<br/>[FR] SYNTHESE DU SYNTHON CETO-ACIDE EN C1-C6 DES EPOTHILONES
  申请人：UNIV MISSISSIPPI

  公开号：WO2005054429A2

  公开（公告）日：2005-06-16

  The present invention relates to alternative methods for producing keto-acid synthons, which are useful for the synthesis of epothilones and analogs and derivatives thereof. A general method according to the present invention broadly comprises performing aldol condensation of a first aldehyde of a general formula: (I) with a carbonyl compound in the form of a ketone or a second aldehyde having a generalized formula: (II) thereby to form a first compound having a generalized formula : (III) and thereafter converting the first compound to a protected keto-`acid synthon of generalized formula: (IV) The present invention is also directed to chemical compounds useful in the synthesis of epothilones and analogs and derivatives thereof and to methods for forming each of these chemical compounds.
• Asymmetric aldol reactions using catalytic d(+)-proline: a new, economic and practical approach to a commonly employed C1–C6 keto-acid synthon of the epothilones
  作者：Yansong Zheng、Mitchell A Avery

  DOI：10.1016/j.tet.2003.12.048

  日期：2004.2

  A new approach to ketoacid 4, a common C1-C6 fragment used in the total synthesis of epothilones was initiated by direct aldol reaction of acetone with a pivaldehyde-like substance 5, catalyzed with D-proline, leading to a 2,6-diketoalcohol with better than 99% ee. Further intramolecular closure of the diketone 8 followed by oxidation of the silyl protected hydroxycyclohexenone 14 led to the desired product 4. None of the steps have been optimized, yet the overall yield for the four-step process is 31%. The use of commercially available D-proline to construct the chiral center of 4 under very mild reaction conditions provided an economical and practical method for its construction. (C) 2004 Elsevier Ltd. All rights reserved.