<2S,2(1R),3S,6R,8S,8(3S),9R>-3,9-Dimethyl-2-<1-methyl-4-<<(1,1-dimethylethyl)diphenylsilyl>oxy>butyl>-8-(3-methyl-4-pentenyl)-1,7-dioxaspiro<5.5>undecane | 152033-16-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: <2S,2(1R),3S,6R,8S,8(3S),9R>-3,9-Dimethyl-2-<1-methyl-4-<<(1,1-dimethylethyl)diphenylsilyl>oxy>butyl>-8-(3-methyl-4-pentenyl)-1,7-dioxaspiro<5.5>undecane
• 英文别名: tert-butyl-[(4R)-4-[(2S,3S,6R,8S,9R)-3,9-dimethyl-8-[(3S)-3-methylpent-4-enyl]-1,7-dioxaspiro[5.5]undecan-2-yl]pentoxy]-diphenylsilane
• CAS: 152033-16-4
• 化学式: C₃₈H₅₈O₃Si
• 分子量: 590.962
• InChiKey: FRHCJKYNDROTGV-PAYLTBBPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.91
• 重原子数：
  42
• 可旋转键数：
  13
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.63
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  <2S,2(1R),3S,6R,8S,8(3S),9R>-3,9-Dimethyl-2-<1-methyl-4-<<(1,1-dimethylethyl)diphenylsilyl>oxy>butyl>-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 、 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 、 三乙基硼氢化锂 、 戴斯-马丁氧化剂 、 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 、 甲苯 、 乙腈 为溶剂， 反应 46.0h， 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：

  2-甲基-5-羟基戊酸内酯 在 吡啶 、 4-二甲氨基吡啶 、 正丁基锂 、 samarium diiodide 、 草酰氯 、 三甲基溴硅烷 、 Raney Ni (W-2) 、 四丁基氟化铵 、 四氯化锡 、 sodium hydride 、 potassium carbonate 、 溶剂黄146 、 二甲基亚砜 、 三乙胺 、 三苯基膦 、 lithium bromide 、 锌 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 0.17h， 生成 <2S,2(1R),3S,6R,8S,8(3S),9R>-3,9-Dimethyl-2-<1-methyl-4-<<(1,1-dimethylethyl)diphenylsilyl>oxy>butyl>-8-(3-methyl-4-pentenyl)-1,7-dioxaspiro<5.5>undecane
  参考文献：
  名称：

  Synthetic study on tautomycin. Stereocontrolled synthesis of C(1)C(18) fragment using a strategy of selective reduction of spiroketal

  摘要：

  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.

  DOI：

  10.1016/s0040-4039(00)74091-3

文献信息

• 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.
• 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.