4-[(3aR,5R,6S,6aR)-2,2-dimethyl-6-(3-methylbut-2-enoxy)-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxol-5-yl]butanal | 163185-29-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-[(3aR,5R,6S,6aR)-2,2-dimethyl-6-(3-methylbut-2-enoxy)-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxol-5-yl]butanal
• CAS: 163185-29-3
• 化学式: C₁₆H₂₆O₅
• 分子量: 298.379
• InChiKey: PWGTZFCYFCLQJO-LXTVHRRPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  21
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  54
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  4-[(3aR,5R,6S,6aR)-2,2-dimethyl-6-(3-methylbut-2-enoxy)-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxol-5-yl]butanal 在 iodonium(di-γ-collidine) perchlorate 、 4 A molecular sieve 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 甲苯 为溶剂， 反应 0.75h， 生成 (3aS,4S,7R,7aS)-4-((2R,6S)-6-Iodomethyl-tetrahydro-pyran-2-yl)-7-isopropenyl-2,2-dimethyl-tetrahydro-[1,3]dioxolo[4,5-c]pyran
  参考文献：
  名称：

  1,2-O-Isopropylidenefuranose Templates for the Synthesis of Complex Cyclic Ethers via Neighboring Group Participation by the Acetal Ring Oxygen

  摘要：

  Novel strategies are described for the direct transformation of C5-allylated-1,2-O-isopropylidene-furanoses into complex cyclic ethers. Reaction of these substrates with iodonium ion under aqueous conditions resulted in the facile formation of 2,5-disubstituted tetrahydrofurans (THF's) containing highly substituted branches, in good to high yields, albeit with modest cis stereoselectivity. A similar result was obtained for the one case of the analogous tetrahydropyran (THP) system that was examined. These reactions presumably proceed via neighboring group participation by the acetal ring oxygen on an iodonium ion-alkene charge transfer complex to give a cyclic oxonium ion, thence a cyclic ether-oxocarbenium ion which undergoes intermolecular capture by water. Under anhydrous conditions, substrates which contained a 3-0-(2'-methyl-2'-buten-4'-yl) substituent led to high yields of adjacently connected THF-THP or THP-THP structures. These products are explainable in terms of a two-step process in which a cyclic ether-oxocarbenium ion, resulting from the initial participation reaction, undergoes nucleophilic capture by the activated alkene. A notable feature of this reaction was that only a single THP isomer was obtained in the second ring forming reaction, presumably a consequence of the cyclic nature of the oxocarbenium ion derived from the 1,2-O-isopropylidene acetal residue.

  DOI：

  10.1021/jo00105a012
• 作为产物：
  描述：

  1,2-O-异亚丙基-alpha-D-呋喃木糖 在 咪唑 、 9-borabicyclo[3.3.1]nonane dimer 、 sodium peroxide 、 偶氮二异丁腈 、 碘 、 四丁基碘化铵 、 sodium hydride 、 三苯基膦 作用下， 以 N,N-二甲基甲酰胺 、 苯 为溶剂， 生成 4-[(3aR,5R,6S,6aR)-2,2-dimethyl-6-(3-methylbut-2-enoxy)-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxol-5-yl]butanal
  参考文献：
  名称：

  Neighboring group activation of acetal cleavage: a novel nonacidic strategy for the tandem formation of cyclic ethers.

  摘要：

  DOI：

  10.1021/ja00050a073

文献信息

• Neighboring group activation of acetal cleavage: a novel nonacidic strategy for the tandem formation of cyclic ethers.
  作者：Simone P. Elvey、David R. Mootoo

  DOI：10.1021/ja00050a073

  日期：1992.11
• 1,2-O-Isopropylidenefuranose Templates for the Synthesis of Complex Cyclic Ethers via Neighboring Group Participation by the Acetal Ring Oxygen
  作者：Weifang Shan、Phyllis Wilson、Wei Liang、David R. Mootoo

  DOI：10.1021/jo00105a012

  日期：1994.12

  Novel strategies are described for the direct transformation of C5-allylated-1,2-O-isopropylidene-furanoses into complex cyclic ethers. Reaction of these substrates with iodonium ion under aqueous conditions resulted in the facile formation of 2,5-disubstituted tetrahydrofurans (THF's) containing highly substituted branches, in good to high yields, albeit with modest cis stereoselectivity. A similar result was obtained for the one case of the analogous tetrahydropyran (THP) system that was examined. These reactions presumably proceed via neighboring group participation by the acetal ring oxygen on an iodonium ion-alkene charge transfer complex to give a cyclic oxonium ion, thence a cyclic ether-oxocarbenium ion which undergoes intermolecular capture by water. Under anhydrous conditions, substrates which contained a 3-0-(2'-methyl-2'-buten-4'-yl) substituent led to high yields of adjacently connected THF-THP or THP-THP structures. These products are explainable in terms of a two-step process in which a cyclic ether-oxocarbenium ion, resulting from the initial participation reaction, undergoes nucleophilic capture by the activated alkene. A notable feature of this reaction was that only a single THP isomer was obtained in the second ring forming reaction, presumably a consequence of the cyclic nature of the oxocarbenium ion derived from the 1,2-O-isopropylidene acetal residue.