(3S,4S,5R)-3,5-Dimethyl-8-<<(1,1-dimethylethyl)diphenylsilyl>oxy>-1-octen-4-ol | 152033-13-1

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (3S,4S,5R)-3,5-Dimethyl-8-<<(1,1-dimethylethyl)diphenylsilyl>oxy>-1-octen-4-ol
• 英文别名: (3S,4S,5R)-8-[tert-butyl(diphenyl)silyl]oxy-3,5-dimethyloct-1-en-4-ol
• CAS: 152033-13-1
• 化学式: C₂₆H₃₈O₂Si
• 分子量: 410.672
• InChiKey: MVVRZWRUENFQRC-SGIRGMQISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.16
• 重原子数：
  29
• 可旋转键数：
  11
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (3S,4S,5R)-3,5-Dimethyl-8-<<(1,1-dimethylethyl)diphenylsilyl>oxy>-1-octen-4-ol 在 bis(acetylacetonate)oxovanadium 、 palladium dichloride 吡啶 、 2,6-二甲基吡啶 、 叔丁基过氧化氢 、 4-二甲氨基吡啶 、 sodium hydroxide 、 重铬酸吡啶 、 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 、 3 A molecular sieve 、 4 A molecular sieve 、 氢氟酸 、 四丁基氟化铵 、 水 、 双氧水 、 氧气 、 三乙基硅基三氟甲磺酸酯 、 四氯化钛 、 三乙基硼氢化锂 、 碳酸氢钠 、 potassium carbonate 、 戴斯-马丁氧化剂 、 二甲基亚砜 、 三乙胺 、 N,N-二异丙基乙胺 、 间氯过氧苯甲酸 、 copper(l) chloride 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 为溶剂， 反应 143.91h， 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 咪唑 、 lithium aluminium tetrahydride 、 草酰氯 、 三氟化硼乙醚 、 对甲苯磺酸 、 二甲基亚砜 、 三乙胺 作用下， 以 甲醇 、 乙醚 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 22.33h， 生成 (3S,4S,5R)-3,5-Dimethyl-8-<<(1,1-dimethylethyl)diphenylsilyl>oxy>-1-octen-4-ol
  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.
• 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.