<2S,2(7E,1R,4S,5S,9S,10R),3S,6R,8S,8(3S),9R>-2-<4,10-Dihydroxy-9-methoxy-1,5,11-trimethyl-6-oxo-7-dodecenyl>-3,9-dimethyl-8-(3-methyl-4-pentenyl)-1,7-dioxaspiro<5.5>undecane | 159563-15-2

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: <2S,2(7E,1R,4S,5S,9S,10R),3S,6R,8S,8(3S),9R>-2-<4,10-Dihydroxy-9-methoxy-1,5,11-trimethyl-6-oxo-7-dodecenyl>-3,9-dimethyl-8-(3-methyl-4-pentenyl)-1,7-dioxaspiro<5.5>undecane
• 英文别名: (E,3R,4S,8S,9S,12R)-12-[(2S,3S,6R,8S,9R)-3,9-dimethyl-8-[(3S)-3-methylpent-4-enyl]-1,7-dioxaspiro[5.5]undecan-2-yl]-3,9-dihydroxy-4-methoxy-2,8-dimethyltridec-5-en-7-one
• CAS: 159563-15-2
• 化学式: C₃₃H₅₈O₆
• 分子量: 550.82
• InChiKey: NJWRBJHANWMRBA-SOZGYJJYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.7
• 重原子数：
  39
• 可旋转键数：
  15
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  85.2
• 氢给体数：
  2
• 氢受体数：
  6

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-Dihydroxy-9-methoxy-1,5,11-trimethyl-6-oxo-7-dodecenyl>-3,9-dimethyl-8-(3-methyl-4-pentenyl)-1,7-dioxaspiro<5.5>undecane 在 4 A molecular sieve 作用下， 以 甲苯 为溶剂， 反应 5.0h， 生成 <2S,2(1R,4S,5R),3S,6R,8S,8(3S),9R>-2-(4-Hydroxy-1,5-dimethyl-6-heptenyl)-3,9-dimethyl-8-(3-methyl-4-pentenyl)-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
• 作为产物：
  描述：

  互变霉素 在 2,6-二甲基吡啶 、 四(三苯基膦)钯 、 氢氟酸 、 三正丁基氢锡 、 potassium carbonate 、 lithium chloride 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 乙腈 为溶剂， 反应 12.67h， 生成 <2S,2(7E,1R,4S,5S,9S,10R),3S,6R,8S,8(3S),9R>-2-<4,10-Dihydroxy-9-methoxy-1,5,11-trimethyl-6-oxo-7-dodecenyl>-3,9-dimethyl-8-(3-methyl-4-pentenyl)-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.