(2S,5R)-5-methyl-4-bromo-3-heptyl-2-(methoxycarbonyl)-2,5-dihydrofuran | 127130-46-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氢呋喃
• 英文名称: (2S,5R)-5-methyl-4-bromo-3-heptyl-2-(methoxycarbonyl)-2,5-dihydrofuran
• 英文别名: methyl (2S,5R)-4-bromo-3-heptyl-5-methyl-2,5-dihydrofuran-2-carboxylate
• CAS: 127130-46-5
• 化学式: C₁₄H₂₃BrO₃
• 分子量: 319.239
• InChiKey: RYNCXTDYDMJKCC-MFKMUULPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  18
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  methyl (2S,4R)-2-hydroxy-3-heptyl-3,4-hexadienecarboxylate 在 N-溴代丁二酰亚胺(NBS) 作用下， 以 二氯甲烷 为溶剂， 以66%的产率得到(2S,5R)-5-methyl-4-bromo-3-heptyl-2-(methoxycarbonyl)-2,5-dihydrofuran
  参考文献：
  名称：

  Synthesis of enantioenriched .alpha.-hydroxy-.alpha.-allenylacetic acids by [2,3] Wittig rearrangement of .alpha.-(propargyloxy)acetates

  摘要：

  Optically active (R)-(propargyloxy)acetic esters 5, available in ca. 90% ee through reduction of alkynones 2 with Chirald-LiAlH4 followed by alkylation with chloroacetic acid and esterification with CH2N2, undergo highly stereoselective [2,3] rearrangement upon treatment with LDA in THF at -78-degrees-C followed by Cp2ZrCl2 to afford alpha-(S)-hydroxy-beta-(R)-allenic esters 7 with complete transfer of chirality and > 90% diastereoselectivity. Upon treatment with TESOTf in Et3N the (R)-(propargyloxy) acetic esters 5 afford the diastereomeric alpha-(R)-hydroxy-beta-(R)-allenic esters 8 stereoselectively. Both hydroxy esters 7 and 8 cyclize stereospecifically to trans- and cis-2,5-dihydrofurans 13-15 and 17-19 upon treatment with AgNO3-CaCO3, PhSeCl, or NBS.

  DOI：

  10.1021/jo00016a020

文献信息

• [2,3]-Wittig rearrangement of nonracemic (propargyloxy)acetic acids and esters. Synthesis of optically active 2,5-dihydrofurans
  作者：James A. Marshall、Xiao Jun Wang

  DOI：10.1021/jo00297a004

  日期：1990.5
• MARSHALL, JAMES A.;WANG, XIAO-JUN, J. ORG. CHEM., 55,(1990) N0, C. 2995-2996
  作者：MARSHALL, JAMES A.、WANG, XIAO-JUN

  DOI：——

  日期：——
• Synthesis of enantioenriched .alpha.-hydroxy-.alpha.-allenylacetic acids by [2,3] Wittig rearrangement of .alpha.-(propargyloxy)acetates
  作者：James A. Marshall、Xiao Jun Wang

  DOI：10.1021/jo00016a020

  日期：1991.8

  Optically active (R)-(propargyloxy)acetic esters 5, available in ca. 90% ee through reduction of alkynones 2 with Chirald-LiAlH4 followed by alkylation with chloroacetic acid and esterification with CH2N2, undergo highly stereoselective [2,3] rearrangement upon treatment with LDA in THF at -78-degrees-C followed by Cp2ZrCl2 to afford alpha-(S)-hydroxy-beta-(R)-allenic esters 7 with complete transfer of chirality and > 90% diastereoselectivity. Upon treatment with TESOTf in Et3N the (R)-(propargyloxy) acetic esters 5 afford the diastereomeric alpha-(R)-hydroxy-beta-(R)-allenic esters 8 stereoselectively. Both hydroxy esters 7 and 8 cyclize stereospecifically to trans- and cis-2,5-dihydrofurans 13-15 and 17-19 upon treatment with AgNO3-CaCO3, PhSeCl, or NBS.