2,4-Dimethoxy-benzoic acid (3R,4S,5R,6R)-4,6-dihydroxy-1-thia-spiro[4.4]non-3-yl ester | 862081-08-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2,4-Dimethoxy-benzoic acid (3R,4S,5R,6R)-4,6-dihydroxy-1-thia-spiro[4.4]non-3-yl ester
• CAS: 862081-08-1
• 化学式: C₁₇H₂₂O₆S
• 分子量: 354.424
• InChiKey: NBHCDQSDCOYVBL-QSJFSLAZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.62
• 重原子数：
  24.0
• 可旋转键数：
  4.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  85.22
• 氢给体数：
  2.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  2,4-Dimethoxy-benzoic acid (3R,4S,5R,6R)-4,6-dihydroxy-1-thia-spiro[4.4]non-3-yl ester 在 吡啶 、 Davis oxaziridine reagent 、 silver nitrate 、 三乙胺 作用下， 以 四氢呋喃 、 氯仿 、 1,2-二氯乙烷 、 乙腈 为溶剂， 反应 35.0h， 生成 2,4-Dimethoxy-benzoic acid (1R,3R,4R,5S,11R)-3-(6-chloro-purin-9-yl)-7,7,9,9-tetraisopropyl-6,8,10-trioxa-2-thia-7,9-disila-tricyclo[9.3.0.01,5]tetradec-4-yl ester
  参考文献：
  名称：

  Stereoselective Synthesis of β-Anomeric 4‘-Thiaspirocyclic Ribonucleosides Carrying the Full Complement of RNA-Level Hydroxyl Substitution

  摘要：

  Stereoselective syntheses of a group of 4'-thiaspirocyclic ribonucleosides featuring both pyrimidine and purine classes and both possible configurations at C-5' are described. Use is made of the Pummerer reaction of substrates carrying an a-oriented 2,4-dimethoxybenzoyloxy substituent at C-2 in order to gain reliable stereocontrol via neighboring group participation. Irrespective of the S or R configuration of the pivotal sulfoxide intermediates, the nucleobase is captured from the beta-face. The competing process is formation of unsaturated sulfoxides, presumably via competing E2-type elimination. Although differences in reactivity between the two stereoisomeric series were noted, the common route has successfully given rise for the first time to desirable beta-anomeric sulfur-containing spiroribonucleosides with minimum formation of the alpha-anomers.

  DOI：

  10.1021/jo0506985
• 作为产物：
  描述：

  (1'R,3aS,4R,6aR)-2,2-dimethylspiro[6,6a-dihydro-3aH-thieno[3,4-d][1,3]dioxole-4,2'-cyclopentane]-1'-ol 在 二正丁基氧化锡 、 溶剂黄146 作用下， 以 甲醇 、 苯 为溶剂， 反应 8.08h， 生成 2,4-Dimethoxy-benzoic acid (3R,4S,5R,6R)-4,6-dihydroxy-1-thia-spiro[4.4]non-3-yl ester
  参考文献：
  名称：

  Stereoselective Synthesis of β-Anomeric 4‘-Thiaspirocyclic Ribonucleosides Carrying the Full Complement of RNA-Level Hydroxyl Substitution

  摘要：

  Stereoselective syntheses of a group of 4'-thiaspirocyclic ribonucleosides featuring both pyrimidine and purine classes and both possible configurations at C-5' are described. Use is made of the Pummerer reaction of substrates carrying an a-oriented 2,4-dimethoxybenzoyloxy substituent at C-2 in order to gain reliable stereocontrol via neighboring group participation. Irrespective of the S or R configuration of the pivotal sulfoxide intermediates, the nucleobase is captured from the beta-face. The competing process is formation of unsaturated sulfoxides, presumably via competing E2-type elimination. Although differences in reactivity between the two stereoisomeric series were noted, the common route has successfully given rise for the first time to desirable beta-anomeric sulfur-containing spiroribonucleosides with minimum formation of the alpha-anomers.

  DOI：

  10.1021/jo0506985