<2S,2(7E,1R,4S,5S,9S,10R),3S,6R,8S,8(3S),9R>-2-<4,10-Bis<(triethylsilyl)oxy>-9-methoxy-1,5,11-trimethyl-6-oxo-7-dodecenyl>-8-<4-<<(trifluoromethyl)sulfonyl>oxy>-3-methyl-4-pentenyl>-3,9-dimethyl-1,7-dioxaspiro<5.5>undecane | 159563-13-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: <2S,2(7E,1R,4S,5S,9S,10R),3S,6R,8S,8(3S),9R>-2-<4,10-Bis<(triethylsilyl)oxy>-9-methoxy-1,5,11-trimethyl-6-oxo-7-dodecenyl>-8-<4-<<(trifluoromethyl)sulfonyl>oxy>-3-methyl-4-pentenyl>-3,9-dimethyl-1,7-dioxaspiro<5.5>undecane
• 英文别名: [(3S)-5-[(2S,3S,6R,8S,9R)-2-[(E,2R,5S,6S,10S,11R)-10-methoxy-6,12-dimethyl-7-oxo-5,11-bis(triethylsilyloxy)tridec-8-en-2-yl]-3,9-dimethyl-1,7-dioxaspiro[5.5]undecan-8-yl]-3-methylpent-1-en-2-yl] trifluoromethanesulfonate
• CAS: 159563-13-0
• 化学式: C₄₆H₈₅F₃O₉SSi₂
• 分子量: 927.408
• InChiKey: GJOICRSFMRWINB-HFKJFWAMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  12.74
• 重原子数：
  61
• 可旋转键数：
  27
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  115
• 氢给体数：
  0
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  <2S,2(7E,1R,4S,5S,9S,10R),3S,6R,8S,8(3S),9R>-2-<4,10-Bis<(triethylsilyl)oxy>-9-methoxy-1,5,11-trimethyl-6-oxo-7-dodecenyl>-8-<4-<<(trifluoromethyl)sulfonyl>oxy>-3-methyl-4-pentenyl>-3,9-dimethyl-1,7-dioxaspiro<5.5>undecane 在 四(三苯基膦)钯 氢氟酸 、 水 、 三正丁基氢锡 、 乙腈 、 lithium chloride 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 生成 (4R)-4-[(2S,3S,6R,8S,9R)-3,9-dimethyl-8-[(3S)-3-methylpent-4-enyl]-1,7-dioxaspiro[5.5]undecan-2-yl]pentanal
  参考文献：
  名称：

  Oikawa, Hideaki; Oikawa, Masato; Ichihara, Akitami, Bioscience, Biotechnology and Biochemistry, 1994, vol. 58, # 10, p. 1933 - 1935

  摘要：

  DOI：
• 作为产物：
  描述：

  互变霉素 在 2,6-二甲基吡啶 、 potassium carbonate 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 5.67h， 生成 <2S,2(7E,1R,4S,5S,9S,10R),3S,6R,8S,8(3S),9R>-2-<4,10-Bis<(triethylsilyl)oxy>-9-methoxy-1,5,11-trimethyl-6-oxo-7-dodecenyl>-8-<4-<<(trifluoromethyl)sulfonyl>oxy>-3-methyl-4-pentenyl>-3,9-dimethyl-1,7-dioxaspiro<5.5>undecane
  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

• Oikawa, Hideaki; Oikawa, Masato; Ichihara, Akitami, Bioscience, Biotechnology and Biochemistry, 1994, vol. 58, # 10, p. 1933 - 1935
  作者：Oikawa, Hideaki、Oikawa, Masato、Ichihara, Akitami、Ubukata, Makoto、Isono, Kiyoshi

  DOI：——

  日期：——
• 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.