7,8-Bis-benzyloxy-6-{1-(tert-butyl-dimethyl-silanyloxy)-4-[3-(tert-butyl-dimethyl-silanyloxy)-1,4,6-trimethoxy-5,8-dioxo-5,8-dihydro-naphthalen-2-yl]-3-oxo-butyl}-1-oxo-1H-isochromene-3-carboxylic acid methyl ester | 908339-15-1

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 异香豆素及其衍生物
• 英文名称: 7,8-Bis-benzyloxy-6-{1-(tert-butyl-dimethyl-silanyloxy)-4-[3-(tert-butyl-dimethyl-silanyloxy)-1,4,6-trimethoxy-5,8-dioxo-5,8-dihydro-naphthalen-2-yl]-3-oxo-butyl}-1-oxo-1H-isochromene-3-carboxylic acid methyl ester
• CAS: 908339-15-1
• 化学式: C₅₄H₆₄O₁₄Si₂
• 分子量: 993.265
• InChiKey: TWHPPRSGRQFTLS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.31
• 重原子数：
  70.0
• 可旋转键数：
  19.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.39
• 拓扑面积：
  172.33
• 氢给体数：
  0.0
• 氢受体数：
  14.0

反应信息

• 作为反应物：
  描述：

  7,8-Bis-benzyloxy-6-{1-(tert-butyl-dimethyl-silanyloxy)-4-[3-(tert-butyl-dimethyl-silanyloxy)-1,4,6-trimethoxy-5,8-dioxo-5,8-dihydro-naphthalen-2-yl]-3-oxo-butyl}-1-oxo-1H-isochromene-3-carboxylic acid methyl ester 在 palladium on activated charcoal 氢气 作用下， 以 乙酸乙酯 为溶剂， 20.0 ℃ 、101.32 kPa 条件下， 反应 12.0h， 以90%的产率得到6-{1-(tert-Butyl-dimethyl-silanyloxy)-4-[3-(tert-butyl-dimethyl-silanyloxy)-1,4,6-trimethoxy-5,8-dioxo-5,8-dihydro-naphthalen-2-yl]-3-oxo-butyl}-7,8-dihydroxy-1-oxo-1H-isochromene-3-carboxylic acid methyl ester
  参考文献：
  名称：

  Investigation of a Convergent Route to Purpuromycin:  Benzofuran Formation vs Spiroketalization

  摘要：

  A mild and efficient [3+2] nitrile oxide/olefin cycloaddition allows coupling of the highly functionalized naphthalene and isocoumarin hemispheres of purpuromycin. A rationale of the inability of advanced keto alcohols to spirocyclize is presented based upon a systematic examination of the electronic factors present in these systems and suggests that the biosynthesis of purpuromycin does not proceed through open-chain intermediates.

  DOI：

  10.1021/ol061112j
• 作为产物：
  描述：

  1,2-苯二羧酸,3,4,6-三甲氧基-,二甲基酯 在 镍 咪唑 、 盐酸 、 甲醇 、 sodium tetrahydroborate 、 lithium aluminium tetrahydride 、 硫酸 、 ammonium acetate 、 水 、 氢气 、 双氧水 、 硼酸 、 sodium hexamethyldisilazane 、 silica gel 、 potassium carbonate 、 戴斯-马丁氧化剂 、 异氰酸苯酯 、 三乙胺 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 氯仿 、 水 、 N,N-二甲基甲酰胺 、 异丙醇 、 丙酮 、 乙腈 、 苯 为溶剂， 20.0 ℃ 、101.33 kPa 条件下， 反应 112.83h， 生成 7,8-Bis-benzyloxy-6-{1-(tert-butyl-dimethyl-silanyloxy)-4-[3-(tert-butyl-dimethyl-silanyloxy)-1,4,6-trimethoxy-5,8-dioxo-5,8-dihydro-naphthalen-2-yl]-3-oxo-butyl}-1-oxo-1H-isochromene-3-carboxylic acid methyl ester
  参考文献：
  名称：

  Investigation of a Convergent Route to Purpuromycin:  Benzofuran Formation vs Spiroketalization

  摘要：

  A mild and efficient [3+2] nitrile oxide/olefin cycloaddition allows coupling of the highly functionalized naphthalene and isocoumarin hemispheres of purpuromycin. A rationale of the inability of advanced keto alcohols to spirocyclize is presented based upon a systematic examination of the electronic factors present in these systems and suggests that the biosynthesis of purpuromycin does not proceed through open-chain intermediates.

  DOI：

  10.1021/ol061112j

文献信息

• Alternative Spiroketalization Methods toward Purpuromycin: A Diketone Approach To Prevent Benzofuran Formation
  作者：Andrew N. Lowell、Michael W. Fennie、Marisa C. Kozlowski

  DOI：10.1021/jo200399z

  日期：2011.8.19

  The central portion of purpuromycin has been assembled via a classical spiroketalization reaction. Key to promoting this reaction mode versus benzofuran formation was the oxidation state of the spiroketal core. With a higher oxidation state, even the electron-deficient isocoumarin found in purpuromycin could be employed directly in the spiroketalization. The two halves of the spiroketalization precursor were joined via a nitrile oxide/styrene 1,3-dipolar cycloaddition. A very mild selenium dioxide oxidation was used to introduce the required oxidation state of the spiroketal core.