(4S)-4-benzyl-3-[(2S,3S,4S,5R)-3,5-dihydroxy-6-[(2S,4R,6S)-4-methoxy-6-methyloxan-2-yl]-2,4-dimethylhexanoyl]-1,3-oxazolidin-2-one | 237056-40-5

• 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: (4S)-4-benzyl-3-[(2S,3S,4S,5R)-3,5-dihydroxy-6-[(2S,4R,6S)-4-methoxy-6-methyloxan-2-yl]-2,4-dimethylhexanoyl]-1,3-oxazolidin-2-one
• CAS: 237056-40-5
• 化学式: C₂₅H₃₇NO₇
• 分子量: 463.571
• InChiKey: SKVKGGCQCUIOAX-JORZDOBBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  33
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  106
• 氢给体数：
  2
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (4S)-4-benzyl-3-[(2S,3S,4S,5R)-3,5-dihydroxy-6-[(2S,4R,6S)-4-methoxy-6-methyloxan-2-yl]-2,4-dimethylhexanoyl]-1,3-oxazolidin-2-one 在 锂硼氢 、 三氟化硼乙醚 、 三正丁基氢锡 、 二异丁基氢化铝 、 戴斯-马丁氧化剂 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 四氢呋喃 、 二氯甲烷 、 甲苯 为溶剂， 反应 45.17h， 生成 S-tert-butyl (2R,3R,4R,5S,6S)-3-hydroxy-8-[(2S,4R,6S)-4-methoxy-6-methyloxan-2-yl]-5-[(4-methoxyphenyl)methoxy]-2,4,6-trimethyloctanethioate
  参考文献：
  名称：

  Synthetic Studies toward the Total Synthesis of Swinholide. 1. Stereoselective Construction of the C₁₉−C₃₅ Subunit

  摘要：

  The development of an approach directed at the total synthesis of the complex cytotoxic marine macrodiolide swinholide is described. The present study focuses on the development of a synthetic route far the preparation of the C-19-C-35 segment of the structure, which is composed of a trisubstituted pyran moiety with a contrathermodynamic anti arrangement of the C-2 and C-6 pyran substituents (swinholide C-27 and C-31) which is joined by an ethano linker to an acyclic array containing five contiguous stereocenters. The pyran subunit was constructed using a stereoselective allylation of a beta-alkoxy aldehyde with 1,3-asymmetric induction and a second stereoselective allylation to prepare the C-glycosidic type of linkage. Use of the Hafner-Duthaler reagent was investigated as a potential means of constructing the anti vicinal hydroxyl-methyl relationships found in the C-19-C-24 Segment but was found not to be practical in this instance. The Evans bis propionate methodology was used to introduce a four-carbon unit, and a Mukaiyama aldol was used for chain extension to incorporate the remaining two carbons and two stereocenters of this segment. Attempted use of the Hanessian benzylidene acetal fragmentation reaction in this sequence was thwarted by neighboring group participation of an oxazolidinone in one case and an unexpected regiochemical outcome in another. The approach developed affords the C19-C35 substructure in 18 steps overall from ethyl acetoacetate and in adequate quantities (10% overall yield) to support the projected total synthesis.

  DOI：

  10.1021/jo990291y
• 作为产物：
  描述：

  (4S,6S)-4-(methoxy)-6-hydroxy-1-heptene 在 2,3-二巯基丁二酸 、 三氟甲磺酸三甲基硅酯 、 四氯化钛 、 臭氧 、 N,N-二异丙基乙胺 、 三苯基膦 、 tetramethylammonium triacetoxyborohydride 作用下， 以 溶剂黄146 、 乙腈 为溶剂， 反应 64.75h， 生成 (4S)-4-benzyl-3-[(2S,3S,4S,5R)-3,5-dihydroxy-6-[(2S,4R,6S)-4-methoxy-6-methyloxan-2-yl]-2,4-dimethylhexanoyl]-1,3-oxazolidin-2-one
  参考文献：
  名称：

  Synthetic Studies toward the Total Synthesis of Swinholide. 1. Stereoselective Construction of the C₁₉−C₃₅ Subunit

  摘要：

  The development of an approach directed at the total synthesis of the complex cytotoxic marine macrodiolide swinholide is described. The present study focuses on the development of a synthetic route far the preparation of the C-19-C-35 segment of the structure, which is composed of a trisubstituted pyran moiety with a contrathermodynamic anti arrangement of the C-2 and C-6 pyran substituents (swinholide C-27 and C-31) which is joined by an ethano linker to an acyclic array containing five contiguous stereocenters. The pyran subunit was constructed using a stereoselective allylation of a beta-alkoxy aldehyde with 1,3-asymmetric induction and a second stereoselective allylation to prepare the C-glycosidic type of linkage. Use of the Hafner-Duthaler reagent was investigated as a potential means of constructing the anti vicinal hydroxyl-methyl relationships found in the C-19-C-24 Segment but was found not to be practical in this instance. The Evans bis propionate methodology was used to introduce a four-carbon unit, and a Mukaiyama aldol was used for chain extension to incorporate the remaining two carbons and two stereocenters of this segment. Attempted use of the Hanessian benzylidene acetal fragmentation reaction in this sequence was thwarted by neighboring group participation of an oxazolidinone in one case and an unexpected regiochemical outcome in another. The approach developed affords the C19-C35 substructure in 18 steps overall from ethyl acetoacetate and in adequate quantities (10% overall yield) to support the projected total synthesis.

  DOI：

  10.1021/jo990291y

文献信息

• Synthetic Studies toward the Total Synthesis of Swinholide. 1. Stereoselective Construction of the C₁₉−C₃₅ Subunit
  作者：Gary E. Keck、Gregory D. Lundquist

  DOI：10.1021/jo990291y

  日期：1999.6.1

  The development of an approach directed at the total synthesis of the complex cytotoxic marine macrodiolide swinholide is described. The present study focuses on the development of a synthetic route far the preparation of the C-19-C-35 segment of the structure, which is composed of a trisubstituted pyran moiety with a contrathermodynamic anti arrangement of the C-2 and C-6 pyran substituents (swinholide C-27 and C-31) which is joined by an ethano linker to an acyclic array containing five contiguous stereocenters. The pyran subunit was constructed using a stereoselective allylation of a beta-alkoxy aldehyde with 1,3-asymmetric induction and a second stereoselective allylation to prepare the C-glycosidic type of linkage. Use of the Hafner-Duthaler reagent was investigated as a potential means of constructing the anti vicinal hydroxyl-methyl relationships found in the C-19-C-24 Segment but was found not to be practical in this instance. The Evans bis propionate methodology was used to introduce a four-carbon unit, and a Mukaiyama aldol was used for chain extension to incorporate the remaining two carbons and two stereocenters of this segment. Attempted use of the Hanessian benzylidene acetal fragmentation reaction in this sequence was thwarted by neighboring group participation of an oxazolidinone in one case and an unexpected regiochemical outcome in another. The approach developed affords the C19-C35 substructure in 18 steps overall from ethyl acetoacetate and in adequate quantities (10% overall yield) to support the projected total synthesis.