<4R,5S,6R(3S,4S,5S)<2R/S-(2-tetrahydropyranyl)oxy>>-4-(<2-<(tert-butyldimethyl)silyl>oxy>ethyl)-6-<(7-<(N,N-diisopropyl)carbamate>-4-hydroxy-5-methyl-1-<<(2-tetrahydropyranyl)oxy>>hept-6-en)-3-yl>-2,2,5-trimethyl<1,3>dioxane | 218274-10-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: <4R,5S,6R(3S,4S,5S)<2R/S-(2-tetrahydropyranyl)oxy>>-4-(<2-<(tert-butyldimethyl)silyl>oxy>ethyl)-6-<(7-<(N,N-diisopropyl)carbamate>-4-hydroxy-5-methyl-1-<<(2-tetrahydropyranyl)oxy>>hept-6-en)-3-yl>-2,2,5-trimethyl<1,3>dioxane
• 英文别名: [(Z,3S,4S,5S)-5-[(4R,5S,6R)-6-[2-[tert-butyl(dimethyl)silyl]oxyethyl]-2,2,5-trimethyl-1,3-dioxan-4-yl]-4-hydroxy-3-methyl-7-(oxan-2-yloxy)hept-1-enyl] N,N-di(propan-2-yl)carbamate
• CAS: 218274-10-3
• 化学式: C₃₅H₆₇NO₈Si
• 分子量: 658.004
• InChiKey: OBEPMLUKXCHGLO-UHPFFHOVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.87
• 重原子数：
  45
• 可旋转键数：
  17
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  95.9
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  <4R,5S,6R(3S,4S,5S)<2R/S-(2-tetrahydropyranyl)oxy>>-4-(<2-<(tert-butyldimethyl)silyl>oxy>ethyl)-6-<(7-<(N,N-diisopropyl)carbamate>-4-hydroxy-5-methyl-1-<<(2-tetrahydropyranyl)oxy>>hept-6-en)-3-yl>-2,2,5-trimethyl<1,3>dioxane 在 咪唑 、 Amberlyst H+ 、 臭氧 作用下， 以 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 72.0h， 生成 <2R,3R,4R,5R,6R(1S,2R)>-5-<2-<(tert-butyldiphenylsilyl)oxy>ethyl>-6-<5-<(tert-butyldiphenylsilyl)oxy>-3-hydroxypent-2-yl>-3-methyltetrahydropyran-2,4-diol
  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：

  Diisopropyl-carbamic acid (Z)-(S)-3-[(4S,5S,6R)-6-(2-hydroxy-ethyl)-2,2,5-trimethyl-[1,3]dioxan-4-yl]-5-(tetrahydro-pyran-2-yloxy)-pent-1-enyl ester 在 咪唑 、 臭氧 作用下， 生成 <4R,5S,6R(3S,4S,5S)<2R/S-(2-tetrahydropyranyl)oxy>>-4-(<2-<(tert-butyldimethyl)silyl>oxy>ethyl)-6-<(7-<(N,N-diisopropyl)carbamate>-4-hydroxy-5-methyl-1-<<(2-tetrahydropyranyl)oxy>>hept-6-en)-3-yl>-2,2,5-trimethyl<1,3>dioxane
  参考文献：
  名称：

  Enantioselective Synthesis of a C1-C9 Moiety of Tylonolide, Tylosin Aglycon

  摘要：

  在制备泰洛新 1 的缩醛泰洛内酯的 C1-C9 东部分 2 的过程中，在第一个关键步骤中，氨基甲酸酯 6 与光学活性醛 5a 和 δ-内酯 5b 之间进行了霍普反应的扩展。后者得到了预期的 7b 加合物，产率为 85%。经过同系化反应后，制备出 C1-C7 片段 14b，并与 N,N-二异丙基氨基甲酸巴豆酯进行第二次烯丙基化反应，得到化合物 16，C1-C9 塔罗内酯分子，收率为 80%。

  DOI：

  10.1055/s-1998-1873