rac-(1S,2R,5S,6R,7S)-2-(tert-butyldimethylsilyloxy)-7-(2-(tert-butyldiphenylsilyloxy)ethyl)-5-methyl-8-oxabicyclo[3.2.1]octane-6-carbaldehyde

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: rac-(1S,2R,5S,6R,7S)-2-(tert-butyldimethylsilyloxy)-7-(2-(tert-butyldiphenylsilyloxy)ethyl)-5-methyl-8-oxabicyclo[3.2.1]octane-6-carbaldehyde
• 英文别名: (1R,2S,5R,6S,7R)-2-[tert-butyl(dimethyl)silyl]oxy-7-[2-[tert-butyl(diphenyl)silyl]oxyethyl]-5-methyl-8-oxabicyclo[3.2.1]octane-6-carbaldehyde
• 化学式: C₃₃H₅₀O₄Si₂
• 分子量: 566.929
• InChiKey: IJLBZPXLDSWIRM-TXQJKFKNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.73
• 重原子数：
  39
• 可旋转键数：
  11
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.61
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  rac-(1S,2R,5S,6R,7S)-2-(tert-butyldimethylsilyloxy)-7-(2-(tert-butyldiphenylsilyloxy)ethyl)-5-methyl-8-oxabicyclo[3.2.1]octane-6-carbaldehyde 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 苯 为溶剂， 反应 12.0h， 生成 rac-(1S,2R,5S,6S,7S)-2-(tert-butyldimethylsilyloxy)-7-(2-(tert-butyldiphenylsilyloxy)ethyl)-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：

  rac-1-((2S,5R,6S)-5-(tert-butyldimethylsilyloxy)-6-(ethylthio)-2-methyltetrahydro-2H-pyran-2-yl)-5-(tertbutyldiphenylsilyloxy)pent-2-yn-1-one 在 吡啶 、 2,6-二甲基吡啶 、 喹啉 、 4-二甲氨基吡啶 、 Lindlar's catalyst 、 水 、 氢气 、 四氯化锡 、 二异丁基氢化铝 、 silver carbonate 、 碘甲烷 作用下， 以 乙醇 、 正己烷 、 二氯甲烷 、 乙腈 为溶剂， 反应 22.25h， 生成 rac-(1S,2R,5S,6R,7S)-2-(tert-butyldimethylsilyloxy)-7-(2-(tert-butyldiphenylsilyloxy)ethyl)-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

文献信息

• Identification of an unexpected 2-oxonia[3,3]sigmatropic rearrangement/aldol pathway in the formation of oxacyclic rings. Total synthesis of (+)-aspergillin PZ
  作者：Stephen M. Canham、Larry E. Overman、Paul S. Tanis

  DOI：10.1016/j.tet.2011.09.079

  日期：2011.12

  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.