(1R,3S,4R,5R,6R)-3-exo-((1'R,2'R)-1'-hydroxy-2',3'-(isopropylidenedioxy)propyl)-5-exo,6-exo-(isopropylidenedioxy)-7-oxabicyclo<2.2.1>heptan-2-one | 125284-30-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧吡喃
• 英文名称: (1R,3S,4R,5R,6R)-3-exo-((1'R,2'R)-1'-hydroxy-2',3'-(isopropylidenedioxy)propyl)-5-exo,6-exo-(isopropylidenedioxy)-7-oxabicyclo<2.2.1>heptan-2-one
• 英文别名: (1S,2S,6S,7S,9R)-9-[(S)-((R)-2,2-Dimethyl-[1,3]dioxolan-4-yl)-hydroxy-methyl]-4,4-dimethyl-3,5,10-trioxa-tricyclo[5.2.1.02,6]decan-8-one；(1S,3R,4S,5S,6S)-3-exo-((1'S,2'R)-1'-hydroxy-2',3'-(isopropylidenedioxy)propyl)-5-exo,6-exo-(isopropylidenedioxy)-7-oxabicyclo<2.2.1>heptan-2-one
• CAS: 125284-30-2；125355-73-9
• 化学式: C₁₅H₂₂O₇
• 分子量: 314.335
• InChiKey: VWEPUCFAKNBKLD-ICEISDIFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.01
• 重原子数：
  22.0
• 可旋转键数：
  2.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  83.45
• 氢给体数：
  1.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  (1R,3S,4R,5R,6R)-3-exo-((1'R,2'R)-1'-hydroxy-2',3'-(isopropylidenedioxy)propyl)-5-exo,6-exo-(isopropylidenedioxy)-7-oxabicyclo<2.2.1>heptan-2-one 在 碳酸氢钠 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 以81%的产率得到(1R,4R,5S,6S,7S)-4-exo-<(1'S,2'R)-1'-Hydroxy-2',3'-(isopropylidenedioxy)propyl>-6-exo,7-exo-(isopropylidenedioxy)-2,8-dioxabicyclo<3.2.1>octan-3-one
  参考文献：
  名称：

  Enantiomerically pure 7-oxabicyclo[2.2.1]hept-5-en-2-yl derivatives (naked sugars) as synthetic intermediates. XII. Highly stereoselective total syntheses of octoses and derivatives

  摘要：

  Mukaiyama cross aldolizations of (R)-2,3-O-isopropylideneglyceraldehyde (10) with (1R,4S,5R,6R)-5-exo, 6-exo-(isopropylidenedioxy)-7-oxabicyclo[2.2.1]heptan-2-one ((+)-8) were highly diastereoselective and led to the corresponding u,u,l or SYNCAT ((+)-11) and u,u,u or ANCAT ((-)-21) aldols, respectively. The results were interpreted in terms of extended open transition state models with (ul,lk) and (ul,ul) topicities, respectively, which minimize steric repulsions. Aldols (+)-11 and (-)-21 were converted into (tert-butyl)dimethylsilyl 6-O-acetyl-2,3:7, 8-di-O-isopropylidene-D-glycero-L-talo-alpha-octofuranosid-5-ulose ((-)-18) and its D-talo diastereomer ((+)-28), respectively. Reduction of (-)-18 with LiEt3BH in THF gave, after deprotection, the known D-threo-L-talo-octose ((-)-4). Reduction of (-)-18 with (i-Bu)2AlH/THF gave, after deprotection, the unknown D-threo-D-allo-octose ((+)-5) with high stereoselectivity. Similarly, the unknown D-erythro-D-talo-octose ((+)-6) and D-erythro-L-allo-octose ((-)-7) were derived from (+)-28 through reduction with LiB(s-Bu)3H and (i-Bu)2AlH, respectively.

  DOI：

  10.1021/jo00003a041
• 作为产物：
  描述：

  (+)-2-<<(tert-butyl)dimethylsilyl>oxy>-5,6-exo-(isopropylidenedioxy)-7-oxabicyclo<2.2.1>hept-2-ene 、 (R)-(+)-2,2-二甲基-1,3-二氧戊环-4-甲醛 在 四氯化钛 作用下， 以 二氯甲烷 为溶剂， 以55%的产率得到(1R,3S,4R,5R,6R)-3-exo-((1'R,2'R)-1'-hydroxy-2',3'-(isopropylidenedioxy)propyl)-5-exo,6-exo-(isopropylidenedioxy)-7-oxabicyclo<2.2.1>heptan-2-one
  参考文献：
  名称：

  Enantiomerically pure 7-oxabicyclo[2.2.1]hept-5-en-2-yl derivatives (naked sugars) as synthetic intermediates. XII. Highly stereoselective total syntheses of octoses and derivatives

  摘要：

  Mukaiyama cross aldolizations of (R)-2,3-O-isopropylideneglyceraldehyde (10) with (1R,4S,5R,6R)-5-exo, 6-exo-(isopropylidenedioxy)-7-oxabicyclo[2.2.1]heptan-2-one ((+)-8) were highly diastereoselective and led to the corresponding u,u,l or SYNCAT ((+)-11) and u,u,u or ANCAT ((-)-21) aldols, respectively. The results were interpreted in terms of extended open transition state models with (ul,lk) and (ul,ul) topicities, respectively, which minimize steric repulsions. Aldols (+)-11 and (-)-21 were converted into (tert-butyl)dimethylsilyl 6-O-acetyl-2,3:7, 8-di-O-isopropylidene-D-glycero-L-talo-alpha-octofuranosid-5-ulose ((-)-18) and its D-talo diastereomer ((+)-28), respectively. Reduction of (-)-18 with LiEt3BH in THF gave, after deprotection, the known D-threo-L-talo-octose ((-)-4). Reduction of (-)-18 with (i-Bu)2AlH/THF gave, after deprotection, the unknown D-threo-D-allo-octose ((+)-5) with high stereoselectivity. Similarly, the unknown D-erythro-D-talo-octose ((+)-6) and D-erythro-L-allo-octose ((-)-7) were derived from (+)-28 through reduction with LiB(s-Bu)3H and (i-Bu)2AlH, respectively.

  DOI：

  10.1021/jo00003a041