methyl (3aR,7S,7aR)-7-[tert-butyl(dimethyl)silyl]oxy-2,2-dimethylspiro[3a,4,7,7a-tetrahydro-[1,3]dioxolo[4,5-c]pyran-6,2'-cyclopropane]-1'-carboxylate | 1451180-00-9

• 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: methyl (3aR,7S,7aR)-7-[tert-butyl(dimethyl)silyl]oxy-2,2-dimethylspiro[3a,4,7,7a-tetrahydro-[1,3]dioxolo[4,5-c]pyran-6,2'-cyclopropane]-1'-carboxylate
• CAS: 1451180-00-9
• 化学式: C₁₈H₃₂O₆Si
• 分子量: 372.534
• InChiKey: RVTMPFDVGQGAHE-FSRUHOLFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.86
• 重原子数：
  25
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.94
• 拓扑面积：
  63.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl (3aR,7S,7aR)-7-[tert-butyl(dimethyl)silyl]oxy-2,2-dimethylspiro[3a,4,7,7a-tetrahydro-[1,3]dioxolo[4,5-c]pyran-6,2'-cyclopropane]-1'-carboxylate 在 N-碘代丁二酰亚胺 、 水 作用下， 以 1,4-二氧六环 为溶剂， 以96%的产率得到
  参考文献：
  名称：

  Ring-Contraction vs Ring-Expansion Reactions of Spiro-cyclopropanecarboxylated Sugars

  摘要：

  Electrophilic ring opening of spiro-cyclopropanecarboxylated sugars followed by reaction with DBU revealed interesting ring-contraction and ring-expansion reactions depending on the substrate and the kind of hydroxyl protective group present adjacent to the Spiro center. A stereoselective method for accessing a new class of carbon chain extended keto-furanoses and C-glycosylated bicyclic compounds is reported.

  DOI：

  10.1021/ol402021e
• 作为产物：
  描述：

  (3aR,5aR,8aR,8bS)-3a-(iodomethyl)-2,2,7,7-tetramethyltetrahydro-5H-bis([1,3]dioxolo)[4,5-b:4',5'-d]pyran 在 dirhodium tetraacetate 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 0.42h， 生成 methyl (3aR,7S,7aR)-7-[tert-butyl(dimethyl)silyl]oxy-2,2-dimethylspiro[3a,4,7,7a-tetrahydro-[1,3]dioxolo[4,5-c]pyran-6,2'-cyclopropane]-1'-carboxylate
  参考文献：
  名称：

  Ring-Contraction vs Ring-Expansion Reactions of Spiro-cyclopropanecarboxylated Sugars

  摘要：

  Electrophilic ring opening of spiro-cyclopropanecarboxylated sugars followed by reaction with DBU revealed interesting ring-contraction and ring-expansion reactions depending on the substrate and the kind of hydroxyl protective group present adjacent to the Spiro center. A stereoselective method for accessing a new class of carbon chain extended keto-furanoses and C-glycosylated bicyclic compounds is reported.

  DOI：

  10.1021/ol402021e

文献信息

• Stereoselective synthesis of 1,6-dioxaspirolactones from spiro-cyclopropanecarboxylated sugars: total synthesis of dihydro-pyrenolide D
  作者：Bandi Ramakrishna、Perali Ramu Sridhar

  DOI：10.1039/c4ra16753h

  日期：——

  efficient method for the stereoselective construction of 1,6-dioxaspiro[4.n]decan-2-one systems (n = 4, 5) from sugar derived spirocyclopropane carboxylic acids involving a one-pot ring-opening and cyclization reaction is revealed. The generality of the methodology and its application in the total synthesis of dihydro-pyrenolide D and 4-epi-dihydro-pyrenolide D are reported.

  1,6-dioxaspiro立体选择性构建的有效方法[4.。揭示了由糖衍生的螺环丙烷羧酸制得的n ] decan-2-one系统（n = 4、5），涉及一锅开环和环化反应。报道了该方法的一般性及其在二氢-吡咯内酯D和4-表-二氢-吡咯内酯D的全合成中的应用。