(2S,3Z)-1,2-bis-O-methylethylidene-3-hexene-1,2,6-triol | 180725-62-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2S,3Z)-1,2-bis-O-methylethylidene-3-hexene-1,2,6-triol
• 英文别名: (Z)-4-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]but-3-en-1-ol
• CAS: 180725-62-6
• 化学式: C₉H₁₆O₃
• 分子量: 172.224
• InChiKey: SDUSDKLEVQTJKZ-NHLYECAPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2S,3Z)-1,2-bis-O-methylethylidene-3-hexene-1,2,6-triol 在 咪唑 、 碘 、 三苯基膦 作用下， 以 乙腈 为溶剂， 反应 4.0h， 以96%的产率得到(2S,3Z)-1,2-bis-O-methylethylidene-6-iodo-3-hexene-1,2-diol
  参考文献：
  名称：

  Samarium(II) Iodide-Mediated Reductive Annulations of Ketones Bearing a Distal Vinyl Epoxide Moiety

  摘要：

  Samarium(II) iodide in the presence of hexamethylphosphoramide (HMPA) efficiently promotes the intramolecular coupling of ketones with distal epoxy olefins. The reaction appears to proceed by a mechanism wherein a ketyl couples with the unsaturated epoxide. Subsequent fragmentation of the epoxide ring in compounds 1a-k yields carbocycles 2a-k with an allyl alcohol side chain in good yields, and often with high diastereoselectivity. When tetramethylguanidine was used as an additive instead of HMPA, the desired carbocycle was obtained in good yield, but the diastereoselectivity was diminished. A palladium(0)-catalyzed SmI2 reaction provided the expected product in modest yield, but the sense of diastereoselectivity was reversed. In the latter case, a different reaction mechanism may be involved. Thus, formation of an allylsamarium species may be invoked, with nucleophilic carbonyl addition leading to the observed facial selectivity.

  DOI：

  10.1021/jo960335s
• 作为产物：
  描述：

  tert-butyl-[(Z)-4-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]but-3-enoxy]-dimethylsilane 在 四丁基氟化铵 、 水 作用下， 以 四氢呋喃 为溶剂， 反应 5.0h， 以74%的产率得到(2S,3Z)-1,2-bis-O-methylethylidene-3-hexene-1,2,6-triol
  参考文献：
  名称：

  Samarium(II) Iodide-Mediated Reductive Annulations of Ketones Bearing a Distal Vinyl Epoxide Moiety

  摘要：

  Samarium(II) iodide in the presence of hexamethylphosphoramide (HMPA) efficiently promotes the intramolecular coupling of ketones with distal epoxy olefins. The reaction appears to proceed by a mechanism wherein a ketyl couples with the unsaturated epoxide. Subsequent fragmentation of the epoxide ring in compounds 1a-k yields carbocycles 2a-k with an allyl alcohol side chain in good yields, and often with high diastereoselectivity. When tetramethylguanidine was used as an additive instead of HMPA, the desired carbocycle was obtained in good yield, but the diastereoselectivity was diminished. A palladium(0)-catalyzed SmI2 reaction provided the expected product in modest yield, but the sense of diastereoselectivity was reversed. In the latter case, a different reaction mechanism may be involved. Thus, formation of an allylsamarium species may be invoked, with nucleophilic carbonyl addition leading to the observed facial selectivity.

  DOI：

  10.1021/jo960335s

文献信息

• Samarium(II) Iodide-Mediated Reductive Annulations of Ketones Bearing a Distal Vinyl Epoxide Moiety
  作者：Gary A. Molander、Sagar R. Shakya

  DOI：10.1021/jo960335s

  日期：1996.1.1

  Samarium(II) iodide in the presence of hexamethylphosphoramide (HMPA) efficiently promotes the intramolecular coupling of ketones with distal epoxy olefins. The reaction appears to proceed by a mechanism wherein a ketyl couples with the unsaturated epoxide. Subsequent fragmentation of the epoxide ring in compounds 1a-k yields carbocycles 2a-k with an allyl alcohol side chain in good yields, and often with high diastereoselectivity. When tetramethylguanidine was used as an additive instead of HMPA, the desired carbocycle was obtained in good yield, but the diastereoselectivity was diminished. A palladium(0)-catalyzed SmI2 reaction provided the expected product in modest yield, but the sense of diastereoselectivity was reversed. In the latter case, a different reaction mechanism may be involved. Thus, formation of an allylsamarium species may be invoked, with nucleophilic carbonyl addition leading to the observed facial selectivity.
• Synthesis of the ABCD Trioxadispiroketal Subunit of Azaspiracid-1:  An Iodoetherification−Dehydroiodination Strategy for Complex Spiroketals
  作者：Xiaohua Li、Jialiang Li、David R. Mootoo

  DOI：10.1021/ol701866v

  日期：2007.10.1

  An unusual spiroketalization strategy in which a hydroxyalkene serves as a precursor to a cyclic enol ether was applied to the synthesis of the ABCD trioxadispiroketal subunit of azaspiracid-1. The trioxadispiroketal product, which represents a double anomeric effect, was obtained as a single trioxadispiroketal diastereomer. A key ploy in the synthesis of the CD segment was the use of a cyclopropane as a synthon for the C-14 methyl group.