(2S,3S)-<<2-(Methoxymethoxy)-3-methyl-5-(phenylthio)-1-pentyl>oxy>(1,1-dimethylethyl)diphenylsilane | 165961-38-6

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: (2S,3S)-<<2-(Methoxymethoxy)-3-methyl-5-(phenylthio)-1-pentyl>oxy>(1,1-dimethylethyl)diphenylsilane
• 英文别名: tert-butyl-[(2S,3S)-2-(methoxymethoxy)-3-methyl-5-phenylsulfanylpentoxy]-diphenylsilane
• CAS: 165961-38-6
• 化学式: C₃₀H₄₀O₃SSi
• 分子量: 508.797
• InChiKey: MTJWREUREZQOEK-ABYGYWHVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.37
• 重原子数：
  35
• 可旋转键数：
  14
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  53
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (2S,3S)-<<2-(Methoxymethoxy)-3-methyl-5-(phenylthio)-1-pentyl>oxy>(1,1-dimethylethyl)diphenylsilane 在 正丁基锂 、 三甲基溴硅烷 、 Raney Ni (W-2) 、 间氯过氧苯甲酸 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 生成 (2S,3S,6R,11R)-3,11-Dimethyl-2-<<<(1,1-dimethylethyl)diphenylsilyl>oxy>methyl>-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
• 作为产物：
  描述：

  (tert-butyldiphenylsilanyloxy)acetaldehyde 在 sodium hydroxide 、 9-borabicyclo[3.3.1]nonane dimer 、 三丁基膦 、 双氧水 、 N,N-二异丙基乙胺 作用下， 以 吡啶 、 二氯甲烷 为溶剂， 生成 (2S,3S)-<<2-(Methoxymethoxy)-3-methyl-5-(phenylthio)-1-pentyl>oxy>(1,1-dimethylethyl)diphenylsilane
  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.