(S)-4-[(1S,5S,6S)-6-(2-{(4R,6S)-6-[2-(tert-Butyl-diphenyl-silanyloxy)-ethyl]-2,2-dimethyl-[1,3]dioxan-4-yl}-ethyl)-5-methyl-2-oxo-cyclohex-3-enyl]-4-trimethylsilanyloxy-butyraldehyde | 138970-80-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (S)-4-[(1S,5S,6S)-6-(2-{(4R,6S)-6-[2-(tert-Butyl-diphenyl-silanyloxy)-ethyl]-2,2-dimethyl-[1,3]dioxan-4-yl}-ethyl)-5-methyl-2-oxo-cyclohex-3-enyl]-4-trimethylsilanyloxy-butyraldehyde
• CAS: 138970-80-6
• 化学式: C₄₀H₆₀O₆Si₂
• 分子量: 693.084
• InChiKey: BRXUJYYCFLHICW-KZCIDTSASA-N

反应信息

• 作为反应物：
  描述：

  (S)-4-[(1S,5S,6S)-6-(2-{(4R,6S)-6-[2-(tert-Butyl-diphenyl-silanyloxy)-ethyl]-2,2-dimethyl-[1,3]dioxan-4-yl}-ethyl)-5-methyl-2-oxo-cyclohex-3-enyl]-4-trimethylsilanyloxy-butyraldehyde 在 Na-naphthalene 、 四氯化钛 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 以71%的产率得到(4R,6R)-4-[2-(tert-Butyl-diphenyl-silanyloxy)-ethyl]-2,2-dimethyl-6-[2-((1R,2R,8aS)-2-methyl-8-trimethylsilanyloxy-1,2,6,7,8,8a-hexahydro-naphthalen-1-yl)-ethyl]-[1,3]dioxane
  参考文献：
  名称：

  New low-valent titanium reagents for dicarbonyl coupling and their use in a general method of annulation

  摘要：

  New low-valent titanium reagents have been prepared by reducing TiCl3 (1 mol) with C8K (2 mol) or by reducing TiCl4 (1 mol) with Na-naphthalene (2.75 mol). Ketones carrying a chain that incorporates a suitably placed oxo function (aldehyde or ketone) undergo intramolecular dicarbonyl coupling to produce a bicyclic compound when treated with an excess (16-17 mol of titanium halide per mol of dicarbonyl compound) of one of these reagents. The procedure works well even for highly oxygenated substrates and constitutes a general method of annulation. Other reducing agents besides C8K or Na-naphthalene are suitable, and a brief examination of Na(Hg) and Na-K alloy was made. The C8K/TiCl3 system was also used to convert a cis-1,2-diol into the corresponding olefin.

  DOI：

  10.1021/jo00022a042