1,1-anhydro-1-C-<6-(hydroxymethyl)-2,4-bis<(triisopropylsilyl)oxy>phenyl>-4,6-O-(tetraisopropyldisiloxane-1,3-diyl)-β-D-glucopyranose | 1053633-15-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异香豆素
• 英文名称: 1,1-anhydro-1-C-<6-(hydroxymethyl)-2,4-bis<(triisopropylsilyl)oxy>phenyl>-4,6-O-(tetraisopropyldisiloxane-1,3-diyl)-β-D-glucopyranose
• 英文别名: 1,1-anhydro-1-C-[6-(hydroxymethyl)-2,4-bis[(triisopropylsilyl)oxy]phenyl]-4,6-O-(tetraisopropyldisiloxane-1,3-diyl)-β-D-glucopyranose；(3S,6'aR,9'R,10'R,10'aS)-2',2',4',4'-tetra(propan-2-yl)-4,6-bis[tri(propan-2-yl)silyloxy]spiro[1H-2-benzofuran-3,8'-6a,9,10,10a-tetrahydro-6H-pyrano[3,2-f][1,3,5,2,4]trioxadisilocine]-9',10'-diol
• CAS: 1053633-15-0
• 化学式: C₄₃H₈₂O₉Si₄
• 分子量: 855.461
• InChiKey: JHTAOLMZIOWJTK-ANDJGHCKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.56
• 重原子数：
  56
• 可旋转键数：
  14
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  105
• 氢给体数：
  2
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  三乙基硅基三氟甲磺酸酯 、 1,1-anhydro-1-C-<6-(hydroxymethyl)-2,4-bis<(triisopropylsilyl)oxy>phenyl>-4,6-O-(tetraisopropyldisiloxane-1,3-diyl)-β-D-glucopyranose 在 吡啶 作用下， 反应 2.0h， 以84%的产率得到1,1-anhydro-1-C-<6-(hydroxymethyl)-2,4-bis<(triisopropylsilyl)oxy>phenyl>-4,6-O-(tetraisopropyldisiloxane-1,3-diyl)-2-O-<(triethylsilyl)oxy>-β-D-glucopyranose
  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：

  3,5-二羟基苯甲酸甲酯 在 吡啶 、 咪唑 、 4-二甲氨基吡啶 、 N-溴代丁二酰亚胺(NBS) 、 lithium aluminium tetrahydride 、 Amberlite IR-120 、 叔丁基锂 作用下， 以 四氯化碳 、 乙醚 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 84.5h， 生成 1,1-anhydro-1-C-<6-(hydroxymethyl)-2,4-bis<(triisopropylsilyl)oxy>phenyl>-4,6-O-(tetraisopropyldisiloxane-1,3-diyl)-β-D-glucopyranose
  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 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).