(2'R,3'S,4R,5S)-(+)-3-(2'-Methyl-3'-hydroxy-6',7'-nonadienoyl)-4-methyl-5-phenyl-2-oxazolidinone

• 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: (2'R,3'S,4R,5S)-(+)-3-(2'-Methyl-3'-hydroxy-6',7'-nonadienoyl)-4-methyl-5-phenyl-2-oxazolidinone
• 化学式: C₂₀H₂₅NO₄
• 分子量: 343.423
• InChiKey: KCNOEVKJIKPFCT-JGJFJBOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  25
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.45
• 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：

  三甲基氯硅烷 、 (2'R,3'S,4R,5S)-(+)-3-(2'-Methyl-3'-hydroxy-6',7'-nonadienoyl)-4-methyl-5-phenyl-2-oxazolidinone 在 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 5.0h， 以84%的产率得到(2'R,3'S,4R,5S)-3-(2'-Methyl-3'-(trimethylsiloxy)-6',7'-nonadienoyl)-4-methyl-5-phenyl-2-oxazolidinone
  参考文献：
  名称：

  Syntheses of the Lower Portions of the Pamamycins from .gamma.-(Silyloxy)allenes Using Stereoselective Cyclization, Reduction, and Aldehyde Addition Methodologies

  摘要：

  The pamamycins are a group of homologous macrodiolides produced by Streptomyces alboniger and Streptomyces aurantiacus JA 4570 which are remarkable for their autoregulatory, antifungal, antibacterial, and anion-transfering activities. The syntheses of the C-1'-C-11' (''lower'') portions of pamamycin-607, pamamycin-649A, pamamycin-635A, pamamycin-649B, and pamamycin-635B as the methyl esters 8 and 10-12 are reported. The C-9'-C-11', portions of these esters were introduced by chelation-controlled allylations of C-8' aldehyde intermediates derived from the C-8' alcohols 9 (whose synthesis has been previously reported) and 13-15 using allyltrimethylsilane in the presence of titanium(IV) chloride. The alcohols 13-15 were synthesized via cis selective cyclizations of the trimethylsilyl ether derivatives of the nonracemic gamma-hydroxy allenes 24, 30, and 31 using a one-pot oxymercuration/transpalladation/methoxycarbonylation reaction followed by a chelation-controlled conjugate reduction of the resulting acrylate intermediates. The gamma-hydroxy allene 24 was synthesized via an enzymatic resolution of the gamma-acetoxy allene 20, and the gamma-hydroxy allenes 30 and 31 were synthesized by asymmetric aldol reactions. During the syntheses of the products 14 and 15, chemoselective hydrolyses and reduction reactions were employed in order to differentiate a C-8' carboxyl group from the C-1' carboxyl group. Starting from simple allenyl alcohol starting materials, overall yields from 2% (in 14 steps, for 10) to 14% (in 9 steps, for 12) were observed for the production of the C-1'-C-11' portions of the pamamycins.

  DOI：

  10.1021/jo00091a037
• 作为产物：
  描述：

  己-4,5-二烯-1-醇 在 正丁基锂 、 potassium acetate 、 magnesium sulfate 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 4.17h， 生成 (2'R,3'S,4R,5S)-(+)-3-(2'-Methyl-3'-hydroxy-6',7'-nonadienoyl)-4-methyl-5-phenyl-2-oxazolidinone
  参考文献：
  名称：

  Syntheses of the Lower Portions of the Pamamycins from .gamma.-(Silyloxy)allenes Using Stereoselective Cyclization, Reduction, and Aldehyde Addition Methodologies

  摘要：

  The pamamycins are a group of homologous macrodiolides produced by Streptomyces alboniger and Streptomyces aurantiacus JA 4570 which are remarkable for their autoregulatory, antifungal, antibacterial, and anion-transfering activities. The syntheses of the C-1'-C-11' (''lower'') portions of pamamycin-607, pamamycin-649A, pamamycin-635A, pamamycin-649B, and pamamycin-635B as the methyl esters 8 and 10-12 are reported. The C-9'-C-11', portions of these esters were introduced by chelation-controlled allylations of C-8' aldehyde intermediates derived from the C-8' alcohols 9 (whose synthesis has been previously reported) and 13-15 using allyltrimethylsilane in the presence of titanium(IV) chloride. The alcohols 13-15 were synthesized via cis selective cyclizations of the trimethylsilyl ether derivatives of the nonracemic gamma-hydroxy allenes 24, 30, and 31 using a one-pot oxymercuration/transpalladation/methoxycarbonylation reaction followed by a chelation-controlled conjugate reduction of the resulting acrylate intermediates. The gamma-hydroxy allene 24 was synthesized via an enzymatic resolution of the gamma-acetoxy allene 20, and the gamma-hydroxy allenes 30 and 31 were synthesized by asymmetric aldol reactions. During the syntheses of the products 14 and 15, chemoselective hydrolyses and reduction reactions were employed in order to differentiate a C-8' carboxyl group from the C-1' carboxyl group. Starting from simple allenyl alcohol starting materials, overall yields from 2% (in 14 steps, for 10) to 14% (in 9 steps, for 12) were observed for the production of the C-1'-C-11' portions of the pamamycins.

  DOI：

  10.1021/jo00091a037

文献信息

• Syntheses of the Lower Portions of the Pamamycins from .gamma.-(Silyloxy)allenes Using Stereoselective Cyclization, Reduction, and Aldehyde Addition Methodologies
  作者：Robert D. Walkup、Sang Woong Kim

  DOI：10.1021/jo00091a037

  日期：1994.6

  The pamamycins are a group of homologous macrodiolides produced by Streptomyces alboniger and Streptomyces aurantiacus JA 4570 which are remarkable for their autoregulatory, antifungal, antibacterial, and anion-transfering activities. The syntheses of the C-1'-C-11' (''lower'') portions of pamamycin-607, pamamycin-649A, pamamycin-635A, pamamycin-649B, and pamamycin-635B as the methyl esters 8 and 10-12 are reported. The C-9'-C-11', portions of these esters were introduced by chelation-controlled allylations of C-8' aldehyde intermediates derived from the C-8' alcohols 9 (whose synthesis has been previously reported) and 13-15 using allyltrimethylsilane in the presence of titanium(IV) chloride. The alcohols 13-15 were synthesized via cis selective cyclizations of the trimethylsilyl ether derivatives of the nonracemic gamma-hydroxy allenes 24, 30, and 31 using a one-pot oxymercuration/transpalladation/methoxycarbonylation reaction followed by a chelation-controlled conjugate reduction of the resulting acrylate intermediates. The gamma-hydroxy allene 24 was synthesized via an enzymatic resolution of the gamma-acetoxy allene 20, and the gamma-hydroxy allenes 30 and 31 were synthesized by asymmetric aldol reactions. During the syntheses of the products 14 and 15, chemoselective hydrolyses and reduction reactions were employed in order to differentiate a C-8' carboxyl group from the C-1' carboxyl group. Starting from simple allenyl alcohol starting materials, overall yields from 2% (in 14 steps, for 10) to 14% (in 9 steps, for 12) were observed for the production of the C-1'-C-11' portions of the pamamycins.