(+)-(1R,2S,3R,4S,5S,6S)-5-exo-benzeneselenyl-6-endo-chloro-3-endo-<(2',3',4',6'-tetra-O-acetyl-α-D-galactopyranosyl)methyl>-7-oxabicyclo<2.2.1>heptan-2-endo-ol | 161596-79-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (+)-(1R,2S,3R,4S,5S,6S)-5-exo-benzeneselenyl-6-endo-chloro-3-endo-<(2',3',4',6'-tetra-O-acetyl-α-D-galactopyranosyl)methyl>-7-oxabicyclo<2.2.1>heptan-2-endo-ol
• CAS: 161596-79-8
• 化学式: C₂₇H₃₃ClO₁₁Se
• 分子量: 647.965
• InChiKey: MKVFTDTXUYWAQE-ZRQDRVKTSA-N

物化性质

• 沸点：
  690.3±55.0 °C(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.69
• 重原子数：
  40.0
• 可旋转键数：
  9.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.63
• 拓扑面积：
  143.89
• 氢给体数：
  1.0
• 氢受体数：
  11.0

反应信息

• 作为反应物：
  描述：

  (+)-(1R,2S,3R,4S,5S,6S)-5-exo-benzeneselenyl-6-endo-chloro-3-endo-<(2',3',4',6'-tetra-O-acetyl-α-D-galactopyranosyl)methyl>-7-oxabicyclo<2.2.1>heptan-2-endo-ol 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 以98%的产率得到(+)-(1R,2S,3R,4S)-6-chloro-3-endo-<(2',3',4',6'-tetra-O-acetyl-α-D-galactopyranosyl)methyl>-7-oxabicyclo<2.2.1>hept-5-en-2-endo-ol
  参考文献：
  名称：

  Synthesis of α-D-(1→3) and α-D-(1→4)-C-linked galactosides of D-mannose derivatives. Conformation of α-C-galactosides.

  摘要：

  Reductive radical alpha-D-galactosidation of 5-exo-(benzeneselenyl)-6-endo-chloro-3-methylidene-7- -oxabicyclo[2.2.1]heptan-2-one with acetobromo-D-galactose, followed by ketone reduction led to (+)-(1R,2S, 3R,4S,5S,6S)-5-exo-(benzeneselenyl)-6-endo-chloro-3-endo-[(2',3',4',6'-tetra-O-acetyl-alpha-D-galactopyranosyl)me- thyl]-7-oxabicyclo[2.2.1]heptan-2-endo-ol which was converted into (+)-methyl 3-deoxy-3-[(alpha-D-galactopyranosyl)methyl]-alpha-D-mannopyranoside (1), (+)-3-deoxy-3-[alpha-D-galactopyranosyl)methyl]-D-mannitol (2) and 4-deoxy-4-[(2',3',4',6'-tetra-O-acetyl-alpha-D-galactopyranosyl)methyl]-2,3,6-tri-O-acetyl-D-mannono-1,5-lactone (3). H-1-MNR data of the alpha-C-galactosides confirmed that their preferred conformations involve antiperiplanar arrangements for the C-linked substrates and bond sigma C(1'),C(2') of the alpha-(1-->3)-C-galactoside unit. The alpha-(1-->3)-C-galactoside of methyl mannopyranoside 1 adopts a conformation similar to that proposed for methyl 3-O-(alpha-D-galactopyranosyl)-alpha-D-mannopyranoside.

  DOI：

  10.1016/s0957-4166(00)86285-0
• 作为产物：
  描述：

  5-benzeneselenyl-6-chloro-3-<(2',3',4',6'-tetra-O-acetyl-α-D-galactopyranosyl)methyl>-7-oxabicyclo<2.2.1>heptan-2-one 在 sodium tetrahydroborate 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 0.17h， 以50%的产率得到(+)-(1S,2R,3S,4R,5R,6R)-5-exo-benzeneselenyl-6-endo-chloro-3-endo-<(2',3',4',6'-tetra-O-acetyl-α-D-galactopyranosyl)methyl>-7-oxabicyclo<2.2.1>heptan-2-endo-ol
  参考文献：
  名称：

  Synthesis of α-D-(1→3) and α-D-(1→4)-C-linked galactosides of D-mannose derivatives. Conformation of α-C-galactosides.

  摘要：

  Reductive radical alpha-D-galactosidation of 5-exo-(benzeneselenyl)-6-endo-chloro-3-methylidene-7- -oxabicyclo[2.2.1]heptan-2-one with acetobromo-D-galactose, followed by ketone reduction led to (+)-(1R,2S, 3R,4S,5S,6S)-5-exo-(benzeneselenyl)-6-endo-chloro-3-endo-[(2',3',4',6'-tetra-O-acetyl-alpha-D-galactopyranosyl)me- thyl]-7-oxabicyclo[2.2.1]heptan-2-endo-ol which was converted into (+)-methyl 3-deoxy-3-[(alpha-D-galactopyranosyl)methyl]-alpha-D-mannopyranoside (1), (+)-3-deoxy-3-[alpha-D-galactopyranosyl)methyl]-D-mannitol (2) and 4-deoxy-4-[(2',3',4',6'-tetra-O-acetyl-alpha-D-galactopyranosyl)methyl]-2,3,6-tri-O-acetyl-D-mannono-1,5-lactone (3). H-1-MNR data of the alpha-C-galactosides confirmed that their preferred conformations involve antiperiplanar arrangements for the C-linked substrates and bond sigma C(1'),C(2') of the alpha-(1-->3)-C-galactoside unit. The alpha-(1-->3)-C-galactoside of methyl mannopyranoside 1 adopts a conformation similar to that proposed for methyl 3-O-(alpha-D-galactopyranosyl)-alpha-D-mannopyranoside.

  DOI：

  10.1016/s0957-4166(00)86285-0