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... | 158466-66-1

• 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: 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...
• 英文别名: 2-O-tert-butyl 4-O-[(3R,4S,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]-5,9-dihydroxy-4-methoxy-2,8-dimethyl-7-oxotridecan-3-yl] 1-O-ethyl (Z,3R)-3-hydroxy-1-methylbut-1-ene-1,2,4-tricarboxylate
• CAS: 158466-66-1
• 化学式: C₄₇H₈₀O₁₄
• 分子量: 869.144
• InChiKey: HVYQVZAKPIINDA-OUPQUTJMSA-N

物化性质

• 沸点：
  883.2±65.0 °C(Predicted)
• 密度：
  1.13±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6
• 重原子数：
  61
• 可旋转键数：
  27
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  201
• 氢给体数：
  3
• 氢受体数：
  14

反应信息

• 作为反应物：
  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 4.0h， 以41%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：

  (叔丁氧基羰基亚甲基)三苯基磷烷 在 吡啶 、 咪唑 、 4-二甲氨基吡啶 、 sodium chlorite 、 sodium periodate 、 sodium dihydrogenphosphate 、 2-甲基-2-丁烯 、 甲基磺酰胺 、 3 A molecular sieve 、 AD-mix-β 、 2,4,6-三氯苯甲酰氯 、 氢氟酸 、 potassium tert-butylate 、 氧气 、 4-甲基苯磺酸吡啶 、 碳酸氢钠 、 戴斯-马丁氧化剂 、 溶剂黄146 、 三乙胺 、 三氟乙酸酐 、 2,3-二氯-5,6-二氰基-1,4-苯醌 、 copper(l) chloride 、 palladium dichloride 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 叔丁醇 为溶剂， 生成 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...
  参考文献：
  名称：

  Total synthesis of tautomycin: Efficient aldol coupling of two large subunits

  摘要：

  The total synthesis of tautomycin 1 has been achieved via key aldol condensati

  DOI：

  10.1016/s0040-4039(00)76974-7

文献信息

• Total synthesis of tautomycin: Efficient aldol coupling of two large subunits
  作者：Hideaki Oikawa、Masato Oikawa、Tohru Ueno、Akitami Ichihara

  DOI：10.1016/s0040-4039(00)76974-7

  日期：1994.7

  The total synthesis of tautomycin 1 has been achieved via key aldol condensati
• 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.