(2R,4R,6S)-2-(ethan-1-al)-4-(dimethoxy)-6-methyltetrahydropyran | 148066-68-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧烷类
• 英文名称: (2R,4R,6S)-2-(ethan-1-al)-4-(dimethoxy)-6-methyltetrahydropyran
• 英文别名: ((2S,4R,6R)-2-methyl-4-methoxytetrahydropyran-6-yl)-ethanal；2-[(2R,4R,6S)-4-methoxy-6-methyloxan-2-yl]acetaldehyde
• CAS: 148066-68-6
• 化学式: C₉H₁₆O₃
• 分子量: 172.224
• InChiKey: ZLFDODBVRBCEOL-XHNCKOQMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2R,4R,6S)-2-(ethan-1-al)-4-(dimethoxy)-6-methyltetrahydropyran 在 palladium on activated charcoal lithium hydroxide 、 草酰氯 、 氢气 作用下， 以 四氢呋喃 、 水 、 乙酸乙酯 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 生成 4-((2S,4R,6S)-4-Methoxy-6-methyl-tetrahydro-pyran-2-yl)-butyryl chloride
  参考文献：
  名称：

  Synthetic Study of Marine Macrolide Swinholide A. Stereocontrolled Synthesis of the C11-C32 Segment.

  摘要：

  swonholide A (1) 的 C24-C32 段 4 是从 (S)-甲基 3-羟基丁酸盐立体选择性合成的，而 C11-C32 段 5 的收敛合成是通过 3 和 4 的立体选择性 aldol 缩合实现的。

  DOI：

  10.1248/cpb.42.2403
• 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 、 臭氧 、 三苯基膦 作用下， 以 乙腈 为溶剂， 反应 14.75h， 生成 (2R,4R,6S)-2-(ethan-1-al)-4-(dimethoxy)-6-methyltetrahydropyran
  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

• The total synthesis of swinholide A. Part 1: A stereocontrolled synthesis of a C19-C32 segment
  作者：Ian Paterson、John G. Cumming、Richard A. Ward、Serge Lamboley

  DOI：10.1016/0040-4020(95)00546-k

  日期：1995.8

  The C19-C32 segment 10 of swinholide A was prepared in 15 steps (8% yield, 82% ds) from (±)-16. Key steps include (i) the Sharpless epoxidation, 16 → 17, (ii) the acetal allylation, 15 → 23, (iii) the anti aldol addition, 13 + 14 → 12, and (iv) the alkene hydroboration, 30 → 31. The swinholides are a series of complex polyketide macrodiolides, which display potent cytotoxicity against a variety of

  从（±）-16分15步（产率为8％，产率为82％ds）制备了Swinholide A的C 19 -C 32链段10。关键步骤包括（i）Sharpless环氧化16 → 17，（ii）乙缩醛烯丙基化15 → 23，（iii）抗羟醛加成13 + 14→12和（iv）烯烃硼氢化30→31。swinholides是一系列复杂的聚酮大环氧化物，对多种人类肿瘤细胞系均显示出强大的细胞毒性。1,2从海洋海绵中分离出的Swinholide A1985年，Carmely和Kashman首次报道了Theonella swinhoei作为抗真菌剂。1使用NMR方法和化学方法
• A stereocontrolled synthesis of a C19-C32 / C17-C30 Segment for swinholide A and misakinolide A, Cytotoxic dimeric macrolides from theonella swinhoei.
  作者：Ian Paterson、John G. Cumming

  DOI：10.1016/s0040-4039(00)78876-9

  日期：1992.5

  The C19-C32/C-17-C30 segment (-)-5 of swinholide A/misakinolide A was prepared in 15 steps (6% yield) from (+/-)-13. Key steps include the Sharpless epoxidation, 13 --> 14, the acetal allylation, 12 --> 16, the anti aldol, 17 + 11 --> 9, and the alkene hydroboration, 19 --> 20.
• 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.
• Synthetic Study of Marine Macrolide Swinholide A. Stereocontrolled Synthesis of the C11-C32 Segment.
  作者：Tadashi NAKATA、Toshiya KOMATSU、Kazuo NAGASAWA

  DOI：10.1248/cpb.42.2403

  日期：——

  The C24-C32 segment 4 of swinholide A (1) was stereoselectively synthesized starting from (S)-methyl 3-hydroxybutyrate, and the convergent synthesis of the C11-C32 segment 5 was accomplished via stereoselective aldol condensation of 3 and 4

  swonholide A (1) 的 C24-C32 段 4 是从 (S)-甲基 3-羟基丁酸盐立体选择性合成的，而 C11-C32 段 5 的收敛合成是通过 3 和 4 的立体选择性 aldol 缩合实现的。