(4R)-3-<(E)-(2R,3R)-3-hydroxy-2-methyl-1-oxo-4-hexen-1-yl>-4-(phenylmethyl)-1,3-oxazolidin-2-one | 131685-56-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 英文名称: (4R)-3-<(E)-(2R,3R)-3-hydroxy-2-methyl-1-oxo-4-hexen-1-yl>-4-(phenylmethyl)-1,3-oxazolidin-2-one
• 英文别名: (4R)-4-benzyl-3-[(E,2R,3S)-3-hydroxy-2-methylhex-4-enoyl]-1,3-oxazolidin-2-one
• CAS: 131685-56-8
• 化学式: C₁₇H₂₁NO₄
• 分子量: 303.358
• InChiKey: OQLQDHILLYSATO-DNTPGZEZSA-N

物化性质

• 沸点：
  489.1±38.0 °C(predicted)
• 密度：
  1.207±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  22
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  66.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (4R)-3-<(E)-(2R,3R)-3-hydroxy-2-methyl-1-oxo-4-hexen-1-yl>-4-(phenylmethyl)-1,3-oxazolidin-2-one 在 lithium hydroxide 、 水 、 双氧水 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 生成 (E,2R,3S)-3-hydroxy-2-methylhex-4-enoic acid
  参考文献：
  名称：

  Assignment of stereochemistry in the oligomycin/rutamycin/cytovaricin family of antibiotics. Asymmetric synthesis of the rutamycin spiroketal synthon

  摘要：

  The absolute stereochemistry of the rutamycin antibiotics 2a,b has been established through asymmetric synthesis of the known degradation product 4. One of the key steps in the assemblage process involves acylation of the metalated hydrazone 6 with the N-methoxy-N-methyl amide 5. Both of these enantiomerically pure intermediates have been prepared in good overall yield and high diastereoselectivity (de > 94%). All absolute stereochemical relationships were established through alkylation and aldol bond constructions using N-acyloxazolidinone chiral auxiliaries. Subjection of 17 to acid hydrolysis/deprotection resulted in loss of protecting groups and subsequent spiroketalization to 19 (80%). Silylation of the secondary alcohol in 19 was followed by a samarium-catalyzed Meerwein-Ponndorf-Verley reduction to provide the equatorial alcohol 20 in excellent yield and stereoselectivity (de = 97%). Control experiments indicate that this surprisingly stereoselective reaction operates under kinetic control and that the observed stereochemical outcome may be the result of coordination of the reactive reducing agent to the axial spiroketal oxygen. Conversion of 20 to triol 4 afforded material that is identical with the rutamycin degradation product in all respects. These results establish that the absolute stereochemistry of the rutamycins is as shown (2a,b).

  DOI：

  10.1021/jo00313a011
• 作为产物：
  描述：

  巴豆醛 、 (R)-(-)-4-苄基-3-丙酰基-2-恶唑烷酮 在 三氟甲磺酸二丁硼 、 三乙胺 作用下， 生成 (4R)-3-<(E)-(2R,3R)-3-hydroxy-2-methyl-1-oxo-4-hexen-1-yl>-4-(phenylmethyl)-1,3-oxazolidin-2-one
  参考文献：
  名称：

  Assignment of stereochemistry in the oligomycin/rutamycin/cytovaricin family of antibiotics. Asymmetric synthesis of the rutamycin spiroketal synthon

  摘要：

  The absolute stereochemistry of the rutamycin antibiotics 2a,b has been established through asymmetric synthesis of the known degradation product 4. One of the key steps in the assemblage process involves acylation of the metalated hydrazone 6 with the N-methoxy-N-methyl amide 5. Both of these enantiomerically pure intermediates have been prepared in good overall yield and high diastereoselectivity (de > 94%). All absolute stereochemical relationships were established through alkylation and aldol bond constructions using N-acyloxazolidinone chiral auxiliaries. Subjection of 17 to acid hydrolysis/deprotection resulted in loss of protecting groups and subsequent spiroketalization to 19 (80%). Silylation of the secondary alcohol in 19 was followed by a samarium-catalyzed Meerwein-Ponndorf-Verley reduction to provide the equatorial alcohol 20 in excellent yield and stereoselectivity (de = 97%). Control experiments indicate that this surprisingly stereoselective reaction operates under kinetic control and that the observed stereochemical outcome may be the result of coordination of the reactive reducing agent to the axial spiroketal oxygen. Conversion of 20 to triol 4 afforded material that is identical with the rutamycin degradation product in all respects. These results establish that the absolute stereochemistry of the rutamycins is as shown (2a,b).

  DOI：

  10.1021/jo00313a011

文献信息

• Total Synthesis of (+)-Ratjadone
  作者：Mathias Christmann、Ulhas Bhatt、Monika Quitschalle、Eckhard Claus、Markus Kalesse

  DOI：10.1002/1521-3773(20001201)39:23<4364::aid-anie4364>3.0.co;2-g

  日期：2000.12.1
• The First Total Synthesis of (+)-Ratjadone
  作者：Ulhas Bhatt、Mathias Christmann、Monika Quitschalle、Eckhard Claus、Markus Kalesse

  DOI：10.1021/jo005768g

  日期：2001.3.1

  The first total synthesis of ratjadone was achieved using a highly convergent approach joining three subunits together with a Wittig olefination and a selective Heck reaction as the pivotal steps. Besides establishing a robust and reliable route for the synthesis of this orphan ligand, the configuration of unknown stereocenters could also be determined. This synthesis not only provides an additional access to a biologically important compound but also enables the synthesis of structural analogues for biological target identification.