(2S,5R,6R)-methyl 5-(tert-butyldiphenylsilyloxy)-6-methoxy-2-methyltetrahydro-2H-pyran-2-carboxylate | 1352577-46-8

• 分子结构分类: 有机化合物
• 英文名称: (2S,5R,6R)-methyl 5-(tert-butyldiphenylsilyloxy)-6-methoxy-2-methyltetrahydro-2H-pyran-2-carboxylate
• CAS: 1352577-46-8
• 化学式: C₂₅H₃₄O₅Si
• 分子量: 442.627
• InChiKey: PRCDDIUVZQSKFC-RQTOMXEWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.65
• 重原子数：
  31.0
• 可旋转键数：
  6.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  53.99
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  (2S,5R,6R)-methyl 5-(tert-butyldiphenylsilyloxy)-6-methoxy-2-methyltetrahydro-2H-pyran-2-carboxylate 在 二异丁基氢化铝 、 水 、 rochelle salt 作用下， 以 乙醚 、 正己烷 、 乙酸乙酯 为溶剂， 反应 15.58h， 以94%的产率得到(2S,5R,6R)-5-(tert-butyldiphenylsilyloxy)-6-methoxy-2-methyltetrahydro-2H-pyran-2-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：

  (S)-methyl 2-methyl-3,4-dihydro-2H-pyran-2-carboxylate 在 咪唑 、 间氯过氧苯甲酸 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 6.0h， 生成 (2S,5R,6R)-methyl 5-(tert-butyldiphenylsilyloxy)-6-methoxy-2-methyltetrahydro-2H-pyran-2-carboxylate
  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