(4R,5R,8S)-5-Hydroxy-4,8-dimethyl-9-decenyl acetate | 165961-43-3

• 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: (4R,5R,8S)-5-Hydroxy-4,8-dimethyl-9-decenyl acetate
• 英文别名: [(4R,5R,8S)-5-hydroxy-4,8-dimethyldec-9-enyl] acetate
• CAS: 165961-43-3
• 化学式: C₁₄H₂₆O₃
• 分子量: 242.359
• InChiKey: WUXGYWUJVPBPAO-YRGRVCCFSA-N

物化性质

• 沸点：
  331.6±42.0 °C(Predicted)
• 密度：
  0.943±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  17
• 可旋转键数：
  10
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (4R,5R,8S)-5-Hydroxy-4,8-dimethyl-9-decenyl acetate 在 bis(acetylacetonate)oxovanadium 、 palladium dichloride 2,6-二甲基吡啶 、 叔丁基过氧化氢 、 4-二甲氨基吡啶 、 重铬酸吡啶 、 正丁基锂 、 samarium diiodide 、 草酰氯 、 三甲基溴硅烷 、 3 A molecular sieve 、 4 A molecular sieve 、 氢氟酸 、 四丁基氟化铵 、 水 、 氧气 、 三乙基硅基三氟甲磺酸酯 、 四氯化钛 、 sodium hydride 、 三乙基硼氢化锂 、 potassium carbonate 、 戴斯-马丁氧化剂 、 二甲基亚砜 、 三乙胺 、 三苯基膦 、 copper(l) chloride 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 正己烷 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 甲苯 、 乙腈 、 苯 为溶剂， 反应 75.25h， 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>-3,9-dimethyl-8-(3-methyl-4-oxopentyl)-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：

  (δR,2R,5S,6S)-δ,5-Dimethyl-6-<<<(1,1-dimethylethyl)diphenylsilyl>oxy>methyl>tetrahydro-2-pyranylbutyl acetate 在 吡啶 、 4-二甲氨基吡啶 、 四丁基氟化铵 、 lithium bromide 、 锌 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 57.5h， 生成 (4R,5R,8S)-5-Hydroxy-4,8-dimethyl-9-decenyl acetate
  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

• Synthetic study on tautomycin. Stereocontrolled synthesis of C(1)C(18) fragment using a strategy of selective reduction of spiroketal
  作者：Masato Oikawa、Hideaki Oikawa、Akitami Ichihara

  DOI：10.1016/s0040-4039(00)74091-3

  日期：1993.7

  A stereocontrolled synthesis of C(1)-C(18) fragment of tautomycin is accomplished employing asymmetric crotylboration, selective reduction of spiroketal, and addition of crotylstannane as the key steps.