3-((S)-1-((tert-butyldimethylsilyl)oxy)-2-propyl)-7,7-dimethyl-4-hydroxy-2-((triisopropylsilyl)oxy)-7,8,9,10-tetrahydrophenanthrene | 171979-72-9

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 3-((S)-1-((tert-butyldimethylsilyl)oxy)-2-propyl)-7,7-dimethyl-4-hydroxy-2-((triisopropylsilyl)oxy)-7,8,9,10-tetrahydrophenanthrene
• 英文别名: 2-[(2R)-1-[tert-butyl(dimethyl)silyl]oxypropan-2-yl]-8,8-dimethyl-3-tri(propan-2-yl)silyloxy-6,7-dihydro-5H-phenanthren-1-ol
• CAS: 171979-72-9
• 化学式: C₃₄H₅₈O₃Si₂
• 分子量: 571.004
• InChiKey: FGEODQNFRVPTEH-VWLOTQADSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.84
• 重原子数：
  39
• 可旋转键数：
  10
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3-((S)-1-((tert-butyldimethylsilyl)oxy)-2-propyl)-7,7-dimethyl-4-hydroxy-2-((triisopropylsilyl)oxy)-7,8,9,10-tetrahydrophenanthrene 在 硫酸 、 四丁基氟化铵 、 氧气 作用下， 以 四氢呋喃 、 乙醇 为溶剂， 反应 40.75h， 生成 隐丹参酮
  参考文献：
  名称：

  Aromatic Annulation Strategy for the Synthesis of Angularly-Fused Diterpenoid Quinones. Total Synthesis of (+)-Neocryptotanshinone, (-)-Cryptotanshinone, Tanshinone IIA, and (.+-.)-Royleanone

  摘要：

  The application of a photochemical aromatic annulation strategy in highly efficient total syntheses of several diterpenoid quinones isolated from the traditional Chinese medicine Dan Shen is reported. The pivotal step in each synthesis involves the assembly of a key tricyclic intermediate via the application of a recently developed ''second-generation'' photochemical aromatic annulation method for the construction of highly substituted aromatic systems. In the total synthesis of neocrypto-tanshinone,;the synthesis of the requisite diazo ketone annulation substrate 7 was achieved using palladium-mediated coupling reactions and an intramolecular Friedel-Crafts cyclization to form key carbon-carbon bonds. The pivotal aromatic annulation reaction was then accomplished by irradiating a solution of the diazo ketone 7 and the readily available siloxyalkyne 6 in benzene at room temperature. The desired tricyclic phenol 16 was produced in 58-65% yield and was then converted to (+)-neocryptotanshinone (1) by treatment with tetra-n-butylammonium fluoride in the presence of oxygen. Cyclization to generate (-)-cryptotanshinone (2) was accomplished in high yield by brief exposure of 1 to an ethanolic solution of concentrated sulfuric acid, and dehydrogenation of 2 with DDQ furnished tanshinone IIA (3). As a further demonstration of the utility of the photochemical aromatic annulation strategy in the construction of angularly-fused diterpenes, the total synthesis of(+/-)-royleanone (4) was also investigated. Irradiation of a solution of the diazo ketone 18 and siloxyalkyne 25 produced the tricyclic intermediate 26, which was converted in two steps to royleanone by desilylation and oxidation.

  DOI：

  10.1021/jo00131a006
• 作为产物：
  描述：

  5-溴-2-甲基-2-戊烯 在 (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride 4-二甲氨基吡啶 、 正丁基锂 、 三氯化铝 、 四甲基乙二胺 、 三氟乙酸2,2,2-三氟乙酯 、 4 A molecular sieve 、 2,4-di-t-butyl-3-methyl phenol 、 四甲基锡 、 三溴化硼 、 三乙胺 、 甲烷磺酰基叠氮化物 、 lithium chloride 、 lithium hexamethyldisilazane 作用下， 以 吡啶 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 苯 为溶剂， -78.0~90.0 ℃ 、344.73 kPa 条件下， 反应 116.5h， 生成 3-((S)-1-((tert-butyldimethylsilyl)oxy)-2-propyl)-7,7-dimethyl-4-hydroxy-2-((triisopropylsilyl)oxy)-7,8,9,10-tetrahydrophenanthrene
  参考文献：
  名称：

  Aromatic Annulation Strategy for the Synthesis of Angularly-Fused Diterpenoid Quinones. Total Synthesis of (+)-Neocryptotanshinone, (-)-Cryptotanshinone, Tanshinone IIA, and (.+-.)-Royleanone

  摘要：

  The application of a photochemical aromatic annulation strategy in highly efficient total syntheses of several diterpenoid quinones isolated from the traditional Chinese medicine Dan Shen is reported. The pivotal step in each synthesis involves the assembly of a key tricyclic intermediate via the application of a recently developed ''second-generation'' photochemical aromatic annulation method for the construction of highly substituted aromatic systems. In the total synthesis of neocrypto-tanshinone,;the synthesis of the requisite diazo ketone annulation substrate 7 was achieved using palladium-mediated coupling reactions and an intramolecular Friedel-Crafts cyclization to form key carbon-carbon bonds. The pivotal aromatic annulation reaction was then accomplished by irradiating a solution of the diazo ketone 7 and the readily available siloxyalkyne 6 in benzene at room temperature. The desired tricyclic phenol 16 was produced in 58-65% yield and was then converted to (+)-neocryptotanshinone (1) by treatment with tetra-n-butylammonium fluoride in the presence of oxygen. Cyclization to generate (-)-cryptotanshinone (2) was accomplished in high yield by brief exposure of 1 to an ethanolic solution of concentrated sulfuric acid, and dehydrogenation of 2 with DDQ furnished tanshinone IIA (3). As a further demonstration of the utility of the photochemical aromatic annulation strategy in the construction of angularly-fused diterpenes, the total synthesis of(+/-)-royleanone (4) was also investigated. Irradiation of a solution of the diazo ketone 18 and siloxyalkyne 25 produced the tricyclic intermediate 26, which was converted in two steps to royleanone by desilylation and oxidation.

  DOI：

  10.1021/jo00131a006

文献信息

• Aromatic Annulation Strategy for the Synthesis of Angularly-Fused Diterpenoid Quinones. Total Synthesis of (+)-Neocryptotanshinone, (-)-Cryptotanshinone, Tanshinone IIA, and (.+-.)-Royleanone
  作者：Rick L. Danheiser、David S. Casebier、Fariborz Firooznia

  DOI：10.1021/jo00131a006

  日期：1995.12

  The application of a photochemical aromatic annulation strategy in highly efficient total syntheses of several diterpenoid quinones isolated from the traditional Chinese medicine Dan Shen is reported. The pivotal step in each synthesis involves the assembly of a key tricyclic intermediate via the application of a recently developed ''second-generation'' photochemical aromatic annulation method for the construction of highly substituted aromatic systems. In the total synthesis of neocrypto-tanshinone,;the synthesis of the requisite diazo ketone annulation substrate 7 was achieved using palladium-mediated coupling reactions and an intramolecular Friedel-Crafts cyclization to form key carbon-carbon bonds. The pivotal aromatic annulation reaction was then accomplished by irradiating a solution of the diazo ketone 7 and the readily available siloxyalkyne 6 in benzene at room temperature. The desired tricyclic phenol 16 was produced in 58-65% yield and was then converted to (+)-neocryptotanshinone (1) by treatment with tetra-n-butylammonium fluoride in the presence of oxygen. Cyclization to generate (-)-cryptotanshinone (2) was accomplished in high yield by brief exposure of 1 to an ethanolic solution of concentrated sulfuric acid, and dehydrogenation of 2 with DDQ furnished tanshinone IIA (3). As a further demonstration of the utility of the photochemical aromatic annulation strategy in the construction of angularly-fused diterpenes, the total synthesis of(+/-)-royleanone (4) was also investigated. Irradiation of a solution of the diazo ketone 18 and siloxyalkyne 25 produced the tricyclic intermediate 26, which was converted in two steps to royleanone by desilylation and oxidation.