Ethyl (2Z,4R)-4-<oxy>-6-hydroxy-2-methyl-3-<(1,1-dimethylethoxy)carbonyl>-2-hexenoate | 158466-57-0

• 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)-4-<oxy>-6-hydroxy-2-methyl-3-<(1,1-dimethylethoxy)carbonyl>-2-hexenoate
• 英文别名: 4-O-tert-butyl 1-O-ethyl (Z)-3-[(1R)-1-[diethyl(propan-2-yl)silyl]oxy-3-hydroxypropyl]-2-methylbut-2-enedioate
• CAS: 158466-57-0
• 化学式: C₂₁H₄₀O₆Si
• 分子量: 416.63
• InChiKey: FXFBGINNYJGHIV-FXBHHXAOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.37
• 重原子数：
  28
• 可旋转键数：
  14
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  82.1
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  Ethyl (2Z,4R)-4-<oxy>-6-hydroxy-2-methyl-3-<(1,1-dimethylethoxy)carbonyl>-2-hexenoate 在 palladium dichloride 吡啶 、 2,6-二甲基吡啶 、 4-二甲氨基吡啶 、 sodium chlorite 、 sodium periodate 、 sodium dihydrogenphosphate 、 2-甲基-2-丁烯 、 氢氟酸 、 水 、 氧气 、 三乙基硅基三氟甲磺酸酯 、 四氯化钛 、 碳酸氢钠 、 potassium carbonate 、 戴斯-马丁氧化剂 、 三乙胺 、 三氟乙酸酐 、 copper(l) chloride 作用下， 以 甲醇 、 乙醚 、 二氯甲烷 、 乙酸乙酯 、 N,N-二甲基甲酰胺 、 甲苯 、 乙腈 、 叔丁醇 为溶剂， 反应 35.26h， 生成 trimethyl (Z,3R)-3-hydroxy-1-methylbut-1-ene-1,2,4-tricarboxylate
  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 、 甲基磺酰胺 、 3 A molecular sieve 、 AD-mix-β 、 potassium tert-butylate 、 4-甲基苯磺酸吡啶 、 戴斯-马丁氧化剂 、 溶剂黄146 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 、 叔丁醇 为溶剂， 生成 Ethyl (2Z,4R)-4-<oxy>-6-hydroxy-2-methyl-3-<(1,1-dimethylethoxy)carbonyl>-2-hexenoate
  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.