(S)-5-((2S,5R,6R)-5-(tert-butyldimethylsilyloxy)-6-methoxy-2-methyltetrahydro-2H-pyran-2-yl)-2,2,3,3,12,12-hexamethyl-11,11-diphenyl-4,10-dioxa-3,11-disilatridec-6-yne | 1352577-47-9

• 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: (S)-5-((2S,5R,6R)-5-(tert-butyldimethylsilyloxy)-6-methoxy-2-methyltetrahydro-2H-pyran-2-yl)-2,2,3,3,12,12-hexamethyl-11,11-diphenyl-4,10-dioxa-3,11-disilatridec-6-yne
• CAS: 1352577-47-9
• 化学式: C₄₀H₆₆O₅Si₃
• 分子量: 711.218
• InChiKey: KWXAWDFBSAGPLO-ZIHLNQIOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.28
• 重原子数：
  48.0
• 可旋转键数：
  11.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  46.15
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  (S)-5-((2S,5R,6R)-5-(tert-butyldimethylsilyloxy)-6-methoxy-2-methyltetrahydro-2H-pyran-2-yl)-2,2,3,3,12,12-hexamethyl-11,11-diphenyl-4,10-dioxa-3,11-disilatridec-6-yne 在 喹啉 、 4-二甲氨基吡啶 、 sodium chlorite 、 sodium dihydrogenphosphate dihydrate 、 2-甲基-2-丁烯 、 Lindlar's catalyst 、 四丁基氟化铵 、 氢气 、 四氯化锡 、 1-羟基苯并三唑 、 溶剂黄146 、 盐酸-N-乙基-Nˊ-(3-二甲氨基丙基)碳二亚胺 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 叔丁醇 为溶剂， 反应 40.25h， 生成 (1S,2S,7S,8S,9R)-9-(tert-butyldimethylsilyloxy)-1-methyl-4,12-dioxa-tricyclo[6.3.1.0(2,7)]dodecan-3-one
  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)-5-(tert-butyldimethylsilyloxy)-6-methoxy-2-methyltetrahydro-2H-pyran-2-carbaldehyde 在 2,6-二甲基吡啶 、 (1S,2R)-(+)-N-methylephedrine 、 zinc trifluoromethanesulfonate 、 三乙胺 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 19.5h， 生成 (S)-5-((2S,5R,6R)-5-(tert-butyldimethylsilyloxy)-6-methoxy-2-methyltetrahydro-2H-pyran-2-yl)-2,2,3,3,12,12-hexamethyl-11,11-diphenyl-4,10-dioxa-3,11-disilatridec-6-yne
  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