1-[(4aR,6R,7S,8S,8aR)-3-methyl-7,8-bis(phenylmethoxy)-6-(phenylmethoxymethyl)-6,7,8,8a-tetrahydro-4aH-pyrano[2,3-b][1,4]oxathiin-2-yl]ethanone | 177496-44-5

• 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: 1-[(4aR,6R,7S,8S,8aR)-3-methyl-7,8-bis(phenylmethoxy)-6-(phenylmethoxymethyl)-6,7,8,8a-tetrahydro-4aH-pyrano[2,3-b][1,4]oxathiin-2-yl]ethanone
• CAS: 177496-44-5
• 化学式: C₃₂H₃₄O₆S
• 分子量: 546.684
• InChiKey: AXWGFRIGTHQRCM-YRMRDQOQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  39
• 可旋转键数：
  11
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.34
• 拓扑面积：
  88.5
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  1-[(4aR,6R,7S,8S,8aR)-3-methyl-7,8-bis(phenylmethoxy)-6-(phenylmethoxymethyl)-6,7,8,8a-tetrahydro-4aH-pyrano[2,3-b][1,4]oxathiin-2-yl]ethanone 在 LiAlH 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 以98%的产率得到1-((4aR,6R,7S,8S,8aR)-7,8-Bis-benzyloxy-6-benzyloxymethyl-3-methyl-6,7,8,8a-tetrahydro-4aH-4,5-dioxa-1-thia-naphthalen-2-yl)-ethanol
  参考文献：
  名称：

  基于新型氧硫嘌呤供体远程激活的立体选择性 2-脱氧-β-O-糖苷合成

  摘要：

  通过合适的 1-glycals 和 3-thioxopentane-2,4-dione 之间的逆电子需求 Diels-Alder 反应制备的稳定的糖融合 1,4-oxathiine 衍生物已转化为不寻常的糖基供体，在“远程激活后” ”，与糖基受体有效反应以提供具有总立体选择性的 2-硫代-β-O-糖苷。几个O-亲核试剂被成功地糖基化。硫的还原去除将 2-硫代-β-O-糖苷转化为相应的 2-脱氧-β-O-糖苷，而不影响异头碳原子的立体化学。

  DOI：

  10.1002/1099-0690(200106)2001:11<2083::aid-ejoc2083>3.0.co;2-t
• 作为产物：
  描述：

  3,4,6-三邻苄基半乳醛 、 3-thiophthalimide-2,4-pentanedione 在 吡啶 作用下， 以 二氯甲烷 为溶剂， 以73%的产率得到1-[(4aR,6R,7S,8S,8aR)-3-methyl-7,8-bis(phenylmethoxy)-6-(phenylmethoxymethyl)-6,7,8,8a-tetrahydro-4aH-pyrano[2,3-b][1,4]oxathiin-2-yl]ethanone
  参考文献：
  名称：

  Capozzi, Giuseppe; Dios, Angeles; Franck, Richard W., Angewandte Chemie, 1996, vol. 108, # 7, p. 805 - 807

  摘要：

  DOI：

文献信息

• Novel Bicylic Donors for the Synthesis of 2-Deoxy-β-Glycosides
  作者：Richard W. Franck、Cecilia H. Marzabadi

  DOI：10.1021/jo971934h

  日期：1998.4.1

  Novel bicyclic glycosyl donors have been prepared by the cycloaddition reaction of glycals with 3-thiono-2,4-pentanedione 17 followed by methylenation of the resulting ketone. Treatment of the heterocyclic donors with triflic acid in the presence of a variety of alcohol accepters leads to the formation of beta-glycosides in good yields and with excellent stereoselectivities. Desulfurization of the C-2 carbon-sulfur bonds gives the corresponding 2-deoxy-beta-glycosides. This method has been extended to the synthesis of glycosidic linkages found in the aureolic acid antibiotics. Tetra-N-butylammonium triflate proved to be a useful additive in these glycosylation reactions, suggesting an important role for triflate anion in stabilizing intermediates which are formed.
• Novel Heterocycloaddition Reaction of Glycals
  作者：Angeles Dios、Aloma Geer、Cecilia H. Marzabadi、Richard W. Franck

  DOI：10.1021/jo981047u

  日期：1998.9.1

  Diacyl thione species 1 has been generated and reacted in situ with both pyranoid and furanoid glycals to form novel [4 + 2] cycloadducts. Factors such as protecting groups and configuration of substituents in the glycals along with medium effects were varied to discover influences on face selectivity and reactivity. A qualitative correlation of reactivity with the HOMO-LUMO gap between the glycal (HOMO) and the heterodienic species (LUMO) is observed. In one example, the isolation of byproducts suggests that the cycloaddition may in fact be stepwise.