18,22,3'-Tris-O-(triethylsilyl)tautomycin | 165961-34-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 18,22,3'-Tris-O-(triethylsilyl)tautomycin
• 英文别名: [(3R,4R,5R,8S,9S,12R)-12-[(2S,3S,6R,8S,9R)-3,9-dimethyl-8-[(3S)-3-methyl-4-oxopentyl]-1,7-dioxaspiro[5.5]undecan-2-yl]-4-methoxy-2,8-dimethyl-7-oxo-5,9-bis(triethylsilyloxy)tridecan-3-yl] (3R)-3-(4-methyl-2,5-dioxofuran-3-yl)-3-triethylsilyloxypropanoate
• CAS: 165961-34-2
• 化学式: C₅₉H₁₀₈O₁₃Si₃
• 分子量: 1109.76
• InChiKey: WUVBODDGUDRFAR-POTWNSACSA-N

物化性质

• 沸点：
  916.6±65.0 °C(Predicted)
• 密度：
  1.04±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  13.87
• 重原子数：
  75
• 可旋转键数：
  36
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  159
• 氢给体数：
  0
• 氢受体数：
  13

反应信息

• 作为反应物：
  描述：

  18,22,3'-Tris-O-(triethylsilyl)tautomycin 在 氢氟酸 作用下， 以 乙腈 为溶剂， 反应 1.0h， 以77%的产率得到互变霉素
  参考文献：
  名称：

  Total Synthesis of Tautomycin

  摘要：

  A convergent stereocontrolled synthesis of the antifungal antibiotic tautomycin, a potent protein phosphatases inhibitor, has been achieved first via key aldol coupling of two large subunits, a right-hand C-1-C-21 ketone and a left-hand aldehyde (left from C-22). The C-1-C-10 segment was synthesized through a remote stereochemical control process using a spiroketal template. After joining with the C-11-C-18 segment, the spiroketal moiety was selectively constructed. Then the right-hand C-1-C-21 ketone was synthesized via Roush asymmetric crotylboration. The left-hand aldehyde was prepared from a C-21-C-26 Segment and a dialkylmaleic anhydride segment. Completely stereoselective assemblage of the two subunits, the right-hand and the left-hand, was achieved by employing the Mukaiyama aldol reaction. Further functional group manipulations including desilylation, oxidation at C-2, and deprotection of tert-butyl ester with concomitant anhydride formation provided tautomycin which was identical with the natural product. As a preliminary study, derivatizations and degradation of the natural product were also examined to support the total synthesis.

  DOI：

  10.1021/jo00121a026
• 作为产物：
  描述：

  Ethyl <2Z,4R,8R,9S,10R,13S,14S,17R,17<2S,3S,6R,8S,8(3S),9R>>-4,10,14-trihydroxy-9-methoxy-2,13,17-trimethyl-3-<(1,1-dimethylethoxy)carbonyl>-8-(1-methylethyl)-17-<3,9-dimethyl-8-(3-methyl-4-oxopentyl)-1,7-dioxaspiro<5.5>undec-2-yl>-6,12-dioxo-7-oxa... 在 2,6-二甲基吡啶 、 三乙基硅基三氟甲磺酸酯 作用下， 以 二氯甲烷 为溶剂， 反应 5.0h， 生成 18,22,3'-Tris-O-(triethylsilyl)tautomycin
  参考文献：
  名称：

  Total Synthesis of Tautomycin

  摘要：

  A convergent stereocontrolled synthesis of the antifungal antibiotic tautomycin, a potent protein phosphatases inhibitor, has been achieved first via key aldol coupling of two large subunits, a right-hand C-1-C-21 ketone and a left-hand aldehyde (left from C-22). The C-1-C-10 segment was synthesized through a remote stereochemical control process using a spiroketal template. After joining with the C-11-C-18 segment, the spiroketal moiety was selectively constructed. Then the right-hand C-1-C-21 ketone was synthesized via Roush asymmetric crotylboration. The left-hand aldehyde was prepared from a C-21-C-26 Segment and a dialkylmaleic anhydride segment. Completely stereoselective assemblage of the two subunits, the right-hand and the left-hand, was achieved by employing the Mukaiyama aldol reaction. Further functional group manipulations including desilylation, oxidation at C-2, and deprotection of tert-butyl ester with concomitant anhydride formation provided tautomycin which was identical with the natural product. As a preliminary study, derivatizations and degradation of the natural product were also examined to support the total synthesis.

  DOI：

  10.1021/jo00121a026

文献信息

• Total Synthesis of Tautomycin
  作者：Masato Oikawa、Tohru Ueno、Hideaki Oikawa、Akitami Ichihara

  DOI：10.1021/jo00121a026

  日期：1995.8

  A convergent stereocontrolled synthesis of the antifungal antibiotic tautomycin, a potent protein phosphatases inhibitor, has been achieved first via key aldol coupling of two large subunits, a right-hand C-1-C-21 ketone and a left-hand aldehyde (left from C-22). The C-1-C-10 segment was synthesized through a remote stereochemical control process using a spiroketal template. After joining with the C-11-C-18 segment, the spiroketal moiety was selectively constructed. Then the right-hand C-1-C-21 ketone was synthesized via Roush asymmetric crotylboration. The left-hand aldehyde was prepared from a C-21-C-26 Segment and a dialkylmaleic anhydride segment. Completely stereoselective assemblage of the two subunits, the right-hand and the left-hand, was achieved by employing the Mukaiyama aldol reaction. Further functional group manipulations including desilylation, oxidation at C-2, and deprotection of tert-butyl ester with concomitant anhydride formation provided tautomycin which was identical with the natural product. As a preliminary study, derivatizations and degradation of the natural product were also examined to support the total synthesis.