(1S,2S,6S,7R)-4,4,10,10-Tetramethyl-3,5,8,11-tetraoxa-tricyclo[5.3.1.0^2,6]undecan-9-one | 136029-22-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1S,2S,6S,7R)-4,4,10,10-Tetramethyl-3,5,8,11-tetraoxa-tricyclo[5.3.1.0^2,6]undecan-9-one
• 英文别名: (1S,2S,6S,7R)-4,4,10,10-tetramethyl-3,5,8,11-tetraoxatricyclo[5.3.1.02,6]undecan-9-one
• CAS: 136029-22-6
• 化学式: C₁₁H₁₆O₅
• 分子量: 228.245
• InChiKey: KLYVXNVKBJPJMB-ULAWRXDQSA-N

物化性质

• 沸点：
  326.9±42.0 °C(Predicted)
• 密度：
  1.172±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.81
• 重原子数：
  16.0
• 可旋转键数：
  0.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  53.99
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  (1S,2S,6S,7R)-4,4,10,10-Tetramethyl-3,5,8,11-tetraoxa-tricyclo[5.3.1.0^2,6]undecan-9-one 在 Nafion 117 、 氢氧化钾 作用下， 以 四氢呋喃 、 四氯化碳 、 水 为溶剂， 反应 252.0h， 生成 (methyl 5-deoxy-5,5-dimethyl-2,3-O-isopropylidene-β-L-ribo-hexofuranosid)uronic acid
  参考文献：
  名称：

  Asymmetric total synthesis of azasugars branched at C-5

  摘要：

  The new azasugars (5-ammonio-1,5-N-anhydro-5,6-dideoxy-5-C-methyl-alpha-beta-L-ribo-hexitol)-1-sulfonate and (5-ammonio-1,5-N-anhydro-5-deoxy-5-C-methyl-alpha-beta-D-talo-hexitol)-1-sulfonate have been derived from (1S,2R,4S)-2-cyano-7-oxabicyclo[2.2.1]hept-5-en-2-yl (1R')-camphanate.

  DOI：

  10.1016/s0040-4039(00)79713-9
• 作为产物：
  描述：

  2,8-dioxabicyclo<2.2.1>octane-6,7-diol-3-one, isopropyl acetal 在 lithium hexamethyldisilazane 作用下， 反应 0.67h， 生成 (1S,2S,6S,7R)-4,4,10,10-Tetramethyl-3,5,8,11-tetraoxa-tricyclo[5.3.1.0^2,6]undecan-9-one
  参考文献：
  名称：

  Asymmetric total synthesis of azasugars branched at C-5

  摘要：

  The new azasugars (5-ammonio-1,5-N-anhydro-5,6-dideoxy-5-C-methyl-alpha-beta-L-ribo-hexitol)-1-sulfonate and (5-ammonio-1,5-N-anhydro-5-deoxy-5-C-methyl-alpha-beta-D-talo-hexitol)-1-sulfonate have been derived from (1S,2R,4S)-2-cyano-7-oxabicyclo[2.2.1]hept-5-en-2-yl (1R')-camphanate.

  DOI：

  10.1016/s0040-4039(00)79713-9

文献信息

• Total, asymmetric synthesis of hexoses and azasugars branched at C(5).
  作者：Jürgen Wagner、Pierre Vogel

  DOI：10.1016/s0040-4020(01)91030-0

  日期：1991.11

  The Diels-Alder adduct (-)-5 (a "naked sugar") of furan to 1-cyanovinyl (1R')-camphanate was converted into (+)-(1R,5S,6S,7S)-6-exo,7-exo-(isopropylidenedioxy)-2,8-dioxabicylo[3.2.1]octan-3-one and into (+)-(1R,5S,6S,7S)-7-endo-(benzyloxy)-6-exo-[(t-butyl)dimethylsilyl]oxy}-2,8-dioxabicyclo[3.2.1]-octan-3-one ((+)-17). Double methylation at C(4) gave the corresponding 5-deoxy-5-C-dimethyl furanurono-6,1-lactones (+)-42 and (+)-19, respectively. Stereoselective and successive methylation and benzyloxymethylation of (+)-(1R,5S,6S,7S)-6-exo,-7-exo-(isopropylidenedioxy)2,8-dioxabicyclo[3.2.1]octan-3-one gave (+)-(1R,4R,5S,6S,7S)4-exo-[(benzyloxy)methyl]-6-exo,7-exo-(isopropylidenedioxy)-4-endo-methyl-2,8-dioxabicyclo[3.2.1]octan-3-one ((+)-9). Highly stereoselective oxydative decarboxylation of lactones (+)-9 and (+)-19 led to 5-C-methyl-alpha-beta-D-talo-hexose ((-)-1) and to 6-deoxy-5-C-methyl-alpha-beta-L-arabino-hexose ((-)-2), respectively. Transformation of lactones (+)-9 and (+)-42 into the corresponding acyl azides and their Curtius rearrangements led to (5-ammonio-1,5-N-anhydro-5-deoxy-5-C-methyl-alpha-beta-D-talo-hexitol)-1-sulfonate ((+)-3) and to (5-ammonio-1,5-N-anhydro-5,6-dideoxy-5-C-methyl-alpha-beta-L-ribo-hexitol)1-sulfonate ((+)-4), respectively.