methyl (3aS,4R,6R,6aS)-6-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyl-3a,4,6,6a-tetrahydrofuro[3,4-d][1,3]dioxole-4-carboxylate | 136449-50-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl (3aS,4R,6R,6aS)-6-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyl-3a,4,6,6a-tetrahydrofuro[3,4-d][1,3]dioxole-4-carboxylate
• CAS: 136449-50-8
• 化学式: C₁₄H₂₂O₇
• 分子量: 302.324
• InChiKey: ULKMOMURHJZLPA-HPENLJRUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  21
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  72.4
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  methyl (3aS,4R,6R,6aS)-6-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyl-3a,4,6,6a-tetrahydrofuro[3,4-d][1,3]dioxole-4-carboxylate 在 sodium azide 、 四溴化碳 、 lithium hexamethyldisilazane 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 Methyl 2,5-anhydro-2-azido-3,4:6,7-di-O-isopropylidene-D-glycero-D-talo-heptonate
  参考文献：
  名称：

  Approach to oxetane and furan nucleosides with an anomeric carbon substituent: Nucleophilic substitution at highly hindered α-bromo-oxetane- and -tetrahydrofuran-carboxylates

  摘要：

  Treatment of oxetane-2-carboxylic esters with lithium hexamethyldisilazide generates anions which can be trapped with carbon tetrabromide to give epimeric 2-bromo-oxetane-2-carboxylic esters which undergo rapid displacement of bromide by azide with clean inversion of configuration. This may provide an approach to the synthesis of oxetane nucleosides possessing a carbon substituent at the anomeric position. An example of similar chemistry applied to tetrahydrofuran-2-carboxylic ester is also reported.

  DOI：

  10.1016/0040-4039(91)80836-u
• 作为产物：
  描述：

  甲醇 、 [(3aR,4R,7S,7aS)-4-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyl-6-oxo-3a,4,7,7a-tetrahydro-[1,3]dioxolo[4,5-c]pyran-7-yl] trifluoromethanesulfonate 在 potassium carbonate 作用下， 以79%的产率得到methyl (3aS,4R,6R,6aS)-6-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyl-3a,4,6,6a-tetrahydrofuro[3,4-d][1,3]dioxole-4-carboxylate
  参考文献：
  名称：

  The ring contraction of δ-lactones with leaving group α-substituents: a strategy for the synthesis of 2,5-disubstituted highly functionalised homochiral tetrahydrofurans

  摘要：

  在碱存在下，用甲醇处理C-2位带有保护基的γ-内酯衍生物，可以得到甲基四氢呋喃-γ-羧酸酯，收率良好到极佳，且C-2和C-5位碳取代基具有高度的立体选择性。

  DOI：

  10.1039/c39920001605

文献信息

• The ring contraction of δ-lactones with leaving group α-substituents: a strategy for the synthesis of 2,5-disubstituted highly functionalised homochiral tetrahydrofurans
  作者：Sik-Man S. Choi、Paul M. Myerscough、Antony J. Fairbanks、Ben M. Skead、Claire J. F. Bichard、Simon J. Mantell、Jong Chan Son、George W. J. Fleet、John Saunders、David Brown

  DOI：10.1039/c39920001605

  日期：——

  Treatment of derivatives of δ-lactones having a leaving group at C-2 with methanol in the presence of base gives methyl tetrahydrofuran-α-carboxylates in good to excellent yield with a high degree of stereocontrol of the carbon substituents at C-2 and C-5.

  在碱存在下，用甲醇处理C-2位带有保护基的γ-内酯衍生物，可以得到甲基四氢呋喃-γ-羧酸酯，收率良好到极佳，且C-2和C-5位碳取代基具有高度的立体选择性。
• Approach to oxetane and furan nucleosides with an anomeric carbon substituent: Nucleophilic substitution at highly hindered α-bromo-oxetane- and -tetrahydrofuran-carboxylates
  作者：S. Choi、D.R. Witty、G.W.J. Fleet、P.L. Myer、R. Storer、C.J. Wailis、D. Watkin、L. Pearce

  DOI：10.1016/0040-4039(91)80836-u

  日期：1991.7

  Treatment of oxetane-2-carboxylic esters with lithium hexamethyldisilazide generates anions which can be trapped with carbon tetrabromide to give epimeric 2-bromo-oxetane-2-carboxylic esters which undergo rapid displacement of bromide by azide with clean inversion of configuration. This may provide an approach to the synthesis of oxetane nucleosides possessing a carbon substituent at the anomeric position. An example of similar chemistry applied to tetrahydrofuran-2-carboxylic ester is also reported.