[(2E,4E,7S,8E,10E,14S)-8,14-dimethyl-7-triethylsilyloxyhexadeca-2,4,8,10-tetraenoyl] 2,4,6-trichlorobenzoate | 169821-97-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [(2E,4E,7S,8E,10E,14S)-8,14-dimethyl-7-triethylsilyloxyhexadeca-2,4,8,10-tetraenoyl] 2,4,6-trichlorobenzoate
• CAS: 169821-97-0
• 化学式: C₃₁H₄₃Cl₃O₄Si
• 分子量: 614.125
• InChiKey: IRKZSRVUMFXUIE-NAFRTZJWSA-N

物化性质

• 沸点：
  642.4±55.0 °C(predicted)
• 密度：
  1.102±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  10.55
• 重原子数：
  39
• 可旋转键数：
  18
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  [(2E,4E,7S,8E,10E,14S)-8,14-dimethyl-7-triethylsilyloxyhexadeca-2,4,8,10-tetraenoyl] 2,4,6-trichlorobenzoate 在 4-二甲氨基吡啶 、 三(二甲氨基)锍二氟三甲基硅酸 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 5.0h， 生成 (+)-papulacandin D
  参考文献：
  名称：

  Total Synthesis and Structural Elucidation of the Antifungal Agent Papulacandin D

  摘要：

  Condensation of the aryllithium reagents, prepared from the bromides 10 and 11 and tert-butyllithium, with lactone 19 and acid-catalyzed spirocyclization gave the papulacandin spiroketals 14 and 15. Subsequent protection using di-tert-butylsilyl bis(trifluoromethanesulfonate) gave the diols 31 and 30. Isoleucine (37) was converted using a double Wittig reaction sequence and propargylation of the intermediate aldehyde 46 into the alkynol 47. Separation of the C-7 epimers of 47 was achieved using kinetic resolution via Sharpless epoxidation. Both alkynol epimers 53 and 57 were converted into the papulacandin side chain esters 65 and 66 using a hydrozirconation and palladium(0)-catalyzed coupling sequence. Comparisons of Mosher ester derivatives of 65 and 66 with the Mosher ester derivative of the natural papulacandin side chain and further degradation were consistent with the stereochemistry of the natural product being 7S,14S. Esterification of the spiroketals with the mixed anhydride 70 and global deprotection gave papulacandin D (1).

  DOI：

  10.1021/jo951895e
• 作为产物：
  描述：

  ethyl (S)-2,8-dimethyl-2(E),4(E)-decadienoate 在 吡啶 、 咪唑 、 4-二甲氨基吡啶 、 manganese(IV) oxide 、 bis-triphenylphosphine-palladium(II) chloride 、 Schwartz's reagent 、 potassium trimethylsilonate 、 二异丁基氢化铝 、 trifluoromethanesulfonic acid anhydride 、 三乙胺 、 锌 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 为溶剂， 反应 41.58h， 生成 [(2E,4E,7S,8E,10E,14S)-8,14-dimethyl-7-triethylsilyloxyhexadeca-2,4,8,10-tetraenoyl] 2,4,6-trichlorobenzoate
  参考文献：
  名称：

  Total Synthesis and Structural Elucidation of the Antifungal Agent Papulacandin D

  摘要：

  Condensation of the aryllithium reagents, prepared from the bromides 10 and 11 and tert-butyllithium, with lactone 19 and acid-catalyzed spirocyclization gave the papulacandin spiroketals 14 and 15. Subsequent protection using di-tert-butylsilyl bis(trifluoromethanesulfonate) gave the diols 31 and 30. Isoleucine (37) was converted using a double Wittig reaction sequence and propargylation of the intermediate aldehyde 46 into the alkynol 47. Separation of the C-7 epimers of 47 was achieved using kinetic resolution via Sharpless epoxidation. Both alkynol epimers 53 and 57 were converted into the papulacandin side chain esters 65 and 66 using a hydrozirconation and palladium(0)-catalyzed coupling sequence. Comparisons of Mosher ester derivatives of 65 and 66 with the Mosher ester derivative of the natural papulacandin side chain and further degradation were consistent with the stereochemistry of the natural product being 7S,14S. Esterification of the spiroketals with the mixed anhydride 70 and global deprotection gave papulacandin D (1).

  DOI：

  10.1021/jo951895e

文献信息

• Total synthesis of the antifungal agent papulacandin D
  作者：Anthony G. M. Barrett、Michael Peña、J. Adam Willardsen

  DOI：10.1039/c39950001147

  日期：——

  Condensation of 2,3,4,6-tetra-O-(trimethylsilyl)-D-gluconolactone with tert-butyl[2-lithio-3,5-di-(triisopropylsilyloxy)benzyloxy]dimethylsilane, protection of the resultant spiroketal with di(tert-butyl)silyl di(trifluoromethanesulfonate), selective O-3′-esterification and deprotection gives papulacandin D.

  2,3,4,6-四-O-(三甲基硅基)-D-葡糖醛内酯与叔丁基[2-锂代-3,5-双(三异丙基硅氧基)苯氧基]二甲基硅烷缩合，所得螺缩酮用二(叔丁基)硅基二(三氟甲磺酸)保护，选择性O-3′-酯化和脱保护得到皮刺芹二酮D。
• Total Synthesis and Structural Elucidation of the Antifungal Agent Papulacandin D
  作者：Anthony G. M. Barrett、Michael Peña、J. Adam Willardsen

  DOI：10.1021/jo951895e

  日期：1996.1.1

  Condensation of the aryllithium reagents, prepared from the bromides 10 and 11 and tert-butyllithium, with lactone 19 and acid-catalyzed spirocyclization gave the papulacandin spiroketals 14 and 15. Subsequent protection using di-tert-butylsilyl bis(trifluoromethanesulfonate) gave the diols 31 and 30. Isoleucine (37) was converted using a double Wittig reaction sequence and propargylation of the intermediate aldehyde 46 into the alkynol 47. Separation of the C-7 epimers of 47 was achieved using kinetic resolution via Sharpless epoxidation. Both alkynol epimers 53 and 57 were converted into the papulacandin side chain esters 65 and 66 using a hydrozirconation and palladium(0)-catalyzed coupling sequence. Comparisons of Mosher ester derivatives of 65 and 66 with the Mosher ester derivative of the natural papulacandin side chain and further degradation were consistent with the stereochemistry of the natural product being 7S,14S. Esterification of the spiroketals with the mixed anhydride 70 and global deprotection gave papulacandin D (1).