(S)-1-(2S,5R,6R-5-(tert-butyldimethylsilyloxy)-6-methoxy-2-methyltetrahydro-2H-pyran-2-yl)-5-(tert-butyldiphenylsilyloxy)pent-2-yn-1-ol | 1352577-31-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧杂环己烷
• 英文名称: (S)-1-(2S,5R,6R-5-(tert-butyldimethylsilyloxy)-6-methoxy-2-methyltetrahydro-2H-pyran-2-yl)-5-(tert-butyldiphenylsilyloxy)pent-2-yn-1-ol
• CAS: 1352577-31-1
• 化学式: C₃₄H₅₂O₅Si₂
• 分子量: 596.955
• InChiKey: ACWPZOJZCMUEBY-ZMFYAOANSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.25
• 重原子数：
  41.0
• 可旋转键数：
  9.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  57.15
• 氢给体数：
  1.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  (S)-1-(2S,5R,6R-5-(tert-butyldimethylsilyloxy)-6-methoxy-2-methyltetrahydro-2H-pyran-2-yl)-5-(tert-butyldiphenylsilyloxy)pent-2-yn-1-ol 在 2,6-二甲基吡啶 、 喹啉 、 Lindlar's catalyst 、 四丁基氟化铵 、 氢气 、 四氯化锡 、 溶剂黄146 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 21.67h， 生成 (1S,2R,5S,6S,7S)-2-(tert-butyldimethylsilyloxy)-7-(2-hydroxyethyl)-5-methyl-8-oxabicyclo[3.2.1]octane-6-carbaldehyde
  参考文献：
  名称：

  Identification of an unexpected 2-oxonia[3,3]sigmatropic rearrangement/aldol pathway in the formation of oxacyclic rings. Total synthesis of (+)-aspergillin PZ

  摘要：

  This paper reports the first unambiguous evidence that the cascade synthesis of tetrahydrofuran-containing oxacyclic molecules depicted in Scheme 12 can take place by a 2-oxonia[3,3]sigmatropic/aldol mechanism rather than by a Prins cyclization/pinacol rearrangement sequence. The 8-oxabicyclo [3.2.1]octyl aldehyde products of this reaction, 20 and 29, were employed to complete the first total synthesis of the structurally remarkable isoindolone alkaloid (+)-aspergillin PZ (1). The lack of activity seen in two tumor cell lines for synthetic (+)-aspergillin PZ calls into question the suggestion that aspergillin PZ, like many aspochalasin diterpenes, might exhibit useful antitumor properties. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2011.09.079
• 作为产物：
  描述：

  (2S,5R,6R)-methyl 5-(tert-butyldimethylsilyloxy)-6-methoxy-2-methyltetrahydro-2H-pyran-2-carboxylate 在 (1S,2R)-(+)-N-methylephedrine 、 zinc trifluoromethanesulfonate 、 二异丁基氢化铝 、 三乙胺 作用下， 以 乙醚 、 正己烷 、 甲苯 为溶剂， 反应 33.91h， 生成 (S)-1-(2S,5R,6R-5-(tert-butyldimethylsilyloxy)-6-methoxy-2-methyltetrahydro-2H-pyran-2-yl)-5-(tert-butyldiphenylsilyloxy)pent-2-yn-1-ol
  参考文献：
  名称：

  Identification of an unexpected 2-oxonia[3,3]sigmatropic rearrangement/aldol pathway in the formation of oxacyclic rings. Total synthesis of (+)-aspergillin PZ

  摘要：

  This paper reports the first unambiguous evidence that the cascade synthesis of tetrahydrofuran-containing oxacyclic molecules depicted in Scheme 12 can take place by a 2-oxonia[3,3]sigmatropic/aldol mechanism rather than by a Prins cyclization/pinacol rearrangement sequence. The 8-oxabicyclo [3.2.1]octyl aldehyde products of this reaction, 20 and 29, were employed to complete the first total synthesis of the structurally remarkable isoindolone alkaloid (+)-aspergillin PZ (1). The lack of activity seen in two tumor cell lines for synthetic (+)-aspergillin PZ calls into question the suggestion that aspergillin PZ, like many aspochalasin diterpenes, might exhibit useful antitumor properties. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2011.09.079