Acetic acid (2R,3R,4S,5S,6S)-3-acetoxy-2-acetoxymethyl-6-[(S)-1-(1-cyclohexylidene-ethyl)-4-trimethylsilanyl-but-3-ynyloxy]-5-iodo-tetrahydro-pyran-4-yl ester | 192438-93-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: Acetic acid (2R,3R,4S,5S,6S)-3-acetoxy-2-acetoxymethyl-6-[(S)-1-(1-cyclohexylidene-ethyl)-4-trimethylsilanyl-but-3-ynyloxy]-5-iodo-tetrahydro-pyran-4-yl ester
• CAS: 192438-93-0
• 化学式: C₂₇H₄₁IO₈Si
• 分子量: 648.608
• InChiKey: SSWWLJWHEBZWIC-PROSLKADSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.88
• 重原子数：
  37.0
• 可旋转键数：
  8.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.74
• 拓扑面积：
  97.36
• 氢给体数：
  0.0
• 氢受体数：
  8.0

反应信息

• 作为反应物：
  描述：

  Acetic acid (2R,3R,4S,5S,6S)-3-acetoxy-2-acetoxymethyl-6-[(S)-1-(1-cyclohexylidene-ethyl)-4-trimethylsilanyl-but-3-ynyloxy]-5-iodo-tetrahydro-pyran-4-yl ester 在 potassium fluoride 、 18-冠醚-6 、 三乙基硼 、 氧气 、 碘乙烷 作用下， 以 正己烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 2.5h， 生成 2(R),3(S),4(R),4a(R),4b(S),8a(S),9a(S)-2-acetoxymethyl-4b-methyl-5,5-cyclohexylen-7-iodo-3,4,4a,4b,5,8,8a,9a-octahydro-2H-pyrano[2,3-b]benzofuran-3,4-diol diacetate
  参考文献：
  名称：

  Polyannulated glycopyranosides via radical-mediated tandem reactions. Stereoselective synthesis of 6·5·6 dioxatricycles via 5-exo-trig, 6-endo-dig mode — III

  摘要：

  A series of C-silylated enynols, e.g. 6-methyl-1-trimethylsilyl-hept-5-en-1-yn-4-ol (rac-A) was prepared and submitted to N-iodosuccinimide mediated iodoalkoxylation of tri-O-acetylglycal. Thanks to the presence of the silyl group the resulting diastereomeric glycosides (S)A(1) and (R)A(1) were readily separated. Triethylborane/oxygen/ethyl iodide promoted iodine transfer afforded doubly annulated glycosides in a 5-eso-trigonal, 6-endo-digonal cascade. The required re-protection of the three acetoxy groups was carried out orthogonally The newly installed iodocyclohexene moiety served as site for further functionalization, which was accomplished by metal-halogen exchange followed by electrophilic capture or by reduction/epoxidation. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4020(97)00518-8
• 作为产物：
  描述：

  2-Cyclohexylidene-6-trimethylsilanyl-hex-5-yn-3-ol 、 乙酰化葡萄烯糖 在 N-碘代丁二酰亚胺 作用下， 以 乙腈 为溶剂， 反应 48.0h， 以500 mg的产率得到Acetic acid (2R,3R,4S,5S,6S)-3-acetoxy-2-acetoxymethyl-6-[(S)-1-(1-cyclohexylidene-ethyl)-4-trimethylsilanyl-but-3-ynyloxy]-5-iodo-tetrahydro-pyran-4-yl ester
  参考文献：
  名称：

  Polyannulated glycopyranosides via radical-mediated tandem reactions. Stereoselective synthesis of 6·5·6 dioxatricycles via 5-exo-trig, 6-endo-dig mode — III

  摘要：

  A series of C-silylated enynols, e.g. 6-methyl-1-trimethylsilyl-hept-5-en-1-yn-4-ol (rac-A) was prepared and submitted to N-iodosuccinimide mediated iodoalkoxylation of tri-O-acetylglycal. Thanks to the presence of the silyl group the resulting diastereomeric glycosides (S)A(1) and (R)A(1) were readily separated. Triethylborane/oxygen/ethyl iodide promoted iodine transfer afforded doubly annulated glycosides in a 5-eso-trigonal, 6-endo-digonal cascade. The required re-protection of the three acetoxy groups was carried out orthogonally The newly installed iodocyclohexene moiety served as site for further functionalization, which was accomplished by metal-halogen exchange followed by electrophilic capture or by reduction/epoxidation. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4020(97)00518-8