(3R,4R)-6-<<(tert-butyldiphenyl)silyl>oxy>-3-methyl-4-<<(triisopropyl)silyl>oxy>hex-1-ene | 220365-97-9

• 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: (3R,4R)-6-<<(tert-butyldiphenyl)silyl>oxy>-3-methyl-4-<<(triisopropyl)silyl>oxy>hex-1-ene
• 英文别名: tert-butyl-[(3R,4R)-4-methyl-3-tri(propan-2-yl)silyloxyhex-5-enoxy]-diphenylsilane
• CAS: 220365-97-9
• 化学式: C₃₂H₅₂O₂Si₂
• 分子量: 524.935
• InChiKey: RFQMLZYIUIEYRU-GRKNLSHJSA-N

物化性质

• 沸点：
  519.365±50.00 °C(Press: 760.00 Torr)(predicted)
• 密度：
  0.943±0.10 g/cm3(Temp: 25 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  8.34
• 重原子数：
  36
• 可旋转键数：
  14
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (3R,4R)-6-<<(tert-butyldiphenyl)silyl>oxy>-3-methyl-4-<<(triisopropyl)silyl>oxy>hex-1-ene 在 臭氧 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 以75%的产率得到(2S,3R)-5-<<(tert-butyldiphenyl)silyl>oxy>-2-methyl-3-<<(triisopropyl)silyl>oxy>pentanal
  参考文献：
  名称：

  Allyltitanates in Stereospecific Additions to Chiral δ-Lactol:  Efficient Enantioselective Route to a Potential Precursor of the C1−C9 Portion of Tylonolide

  摘要：

  The Hoppe reaction, which is an allylation reaction of aldehydes using an optically active titanated crotyl carbamate intermediate generated from the corresponding N,N-diisopropyl crotyl carbamate with n-BuLi/(-)-sparteine, was in most cases applied to achiral aldehydes. In this work an extension of this reaction is reported using a racemic gamma-alkoxy allyltitanate (17) and an optically active aldehyde (16) to deliver in good yield the anti adduct 18 as the major isomer. When the corresponding delta-lactol 24 was used in place of aldehyde 16, the anti adduct 25 was obtained in 94% yield as the only product. Structural modifications effected on 25 delivered aldehyde 28 which was in turn submitted to a second allylation reaction in the presence of the optically active titanated crotyl carbamate 2, prepared as described by Hoppe from crotyl carbamate 1, to conduct to compound 29 in 80% yield. This derivative corresponds to a potential precursor of the C1-C9 portion of Tylonolide, aglycon of Tylosin (4).

  DOI：

  10.1021/jo9807722
• 作为产物：
  描述：

  3-(tert-butyldiphenylsilyloxy)-1-propanal 在 2,6-二甲基吡啶 、 正丁基锂 、 三氟化硼乙醚 、 potassium tert-butylate 、 (-)-B-甲氧基二异松莰基硼烷 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 6.5h， 生成 (3R,4R)-6-<<(tert-butyldiphenyl)silyl>oxy>-3-methyl-4-<<(triisopropyl)silyl>oxy>hex-1-ene
  参考文献：
  名称：

  Allyltitanates in Stereospecific Additions to Chiral δ-Lactol:  Efficient Enantioselective Route to a Potential Precursor of the C1−C9 Portion of Tylonolide

  摘要：

  The Hoppe reaction, which is an allylation reaction of aldehydes using an optically active titanated crotyl carbamate intermediate generated from the corresponding N,N-diisopropyl crotyl carbamate with n-BuLi/(-)-sparteine, was in most cases applied to achiral aldehydes. In this work an extension of this reaction is reported using a racemic gamma-alkoxy allyltitanate (17) and an optically active aldehyde (16) to deliver in good yield the anti adduct 18 as the major isomer. When the corresponding delta-lactol 24 was used in place of aldehyde 16, the anti adduct 25 was obtained in 94% yield as the only product. Structural modifications effected on 25 delivered aldehyde 28 which was in turn submitted to a second allylation reaction in the presence of the optically active titanated crotyl carbamate 2, prepared as described by Hoppe from crotyl carbamate 1, to conduct to compound 29 in 80% yield. This derivative corresponds to a potential precursor of the C1-C9 portion of Tylonolide, aglycon of Tylosin (4).

  DOI：

  10.1021/jo9807722