<2S,2(1R,4S,5S),3S,6R,8S,8(3S),9R>-2-<4-<(Triethylsilyl)oxy>-1,5-dimethyl-6-oxoheptyl>-3,9-dimethyl-8-(3-methyl-4-pentenyl)-1,7-dioxaspiro<5.5>undecane | 158466-64-9

• 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,5S),3S,6R,8S,8(3S),9R>-2-<4-<(Triethylsilyl)oxy>-1,5-dimethyl-6-oxoheptyl>-3,9-dimethyl-8-(3-methyl-4-pentenyl)-1,7-dioxaspiro<5.5>undecane
• 英文别名: (3S,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-methyl-4-triethylsilyloxyoctan-2-one
• CAS: 158466-64-9
• 化学式: C₃₂H₆₀O₄Si
• 分子量: 536.911
• InChiKey: YFBQVWVRBDKLJJ-YRGUEPOUSA-N

物化性质

• 沸点：
  561.3±30.0 °C(Predicted)
• 密度：
  0.95±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  8.95
• 重原子数：
  37
• 可旋转键数：
  15
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  <2S,2(1R,4S,5S),3S,6R,8S,8(3S),9R>-2-<4-<(Triethylsilyl)oxy>-1,5-dimethyl-6-oxoheptyl>-3,9-dimethyl-8-(3-methyl-4-pentenyl)-1,7-dioxaspiro<5.5>undecane 在 palladium dichloride 2,6-二甲基吡啶 、 氢氟酸 、 水 、 氧气 、 三乙基硅基三氟甲磺酸酯 、 四氯化钛 、 三乙胺 、 copper(l) chloride 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 27.0h， 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：

  (4R)-4-[(2S,3S,6R,8S,9R)-3,9-dimethyl-8-[(3S)-3-methylpent-4-enyl]-1,7-dioxaspiro[5.5]undecan-2-yl]pentanal 在 bis(acetylacetonate)oxovanadium 叔丁基过氧化氢 、 4-二甲氨基吡啶 、 重铬酸吡啶 、 3 A molecular sieve 、 4 A molecular sieve 、 三乙基硼氢化锂 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 甲苯 为溶剂， 反应 13.5h， 生成 <2S,2(1R,4S,5S),3S,6R,8S,8(3S),9R>-2-<4-<(Triethylsilyl)oxy>-1,5-dimethyl-6-oxoheptyl>-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

• 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.