<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 | 166239-64-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: <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
• 英文别名: (3R,4S,7R)-7-[(2S,3S,6R,8S,9R)-3,9-dimethyl-8-[(3S)-3-methylpent-4-enyl]-1,7-dioxaspiro[5.5]undecan-2-yl]-3-methyloct-1-en-4-ol
• CAS: 166239-64-1
• 化学式: C₂₆H₄₆O₃
• 分子量: 406.649
• InChiKey: UYNZYNDGEWPYDT-QEBSHINZSA-N

物化性质

• 沸点：
  491.2±20.0 °C(Predicted)
• 密度：
  0.96±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.1
• 重原子数：
  29
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  <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 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 、 3 A molecular sieve 、 氢氟酸 、 水 、 氧气 、 三乙基硅基三氟甲磺酸酯 、 四氯化钛 、 三乙基硼氢化锂 、 三乙胺 、 copper(l) chloride 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 36.5h， 生成 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：

  Ethyl (4R)-5-(Tetrahydropyran-2-yloxy)-4-methylpentanoate 在 吡啶 、 咪唑 、 sodium hydroxide 、 lithium aluminium tetrahydride 、 9-borabicyclo[3.3.1]nonane dimer 、 正丁基锂 、 samarium diiodide 、 草酰氯 、 三甲基溴硅烷 、 三丁基膦 、 4 A molecular sieve 、 三氟化硼乙醚 、 四丁基氟化铵 、 双氧水 、 碳酸氢钠 、 potassium carbonate 、 戴斯-马丁氧化剂 、 对甲苯磺酸 、 二甲基亚砜 、 三乙胺 、 N,N-二异丙基乙胺 、 间氯过氧苯甲酸 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 为溶剂， 反应 129.74h， 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