(2S,3R)-5-<<(tert-butyldiphenyl)silyl>oxy>-2-methyl-3-<<(triisopropyl)silyl>oxy>pentanal | 220365-98-0

• 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: (2S,3R)-5-<<(tert-butyldiphenyl)silyl>oxy>-2-methyl-3-<<(triisopropyl)silyl>oxy>pentanal
• 英文别名: (2S,3R)-5-[tert-butyl(diphenyl)silyl]oxy-2-methyl-3-tri(propan-2-yl)silyloxypentanal
• CAS: 220365-98-0
• 化学式: C₃₁H₅₀O₃Si₂
• 分子量: 526.907
• InChiKey: XLICPTYMYDUSOC-POURPWNDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.35
• 重原子数：
  36
• 可旋转键数：
  14
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2E)-1-{[(N,N-diisopropyl)carbamoyl]oxy}-5-[(2-tetrahydropyranyl)oxy]pent-2-ene 、 (2S,3R)-5-<<(tert-butyldiphenyl)silyl>oxy>-2-methyl-3-<<(triisopropyl)silyl>oxy>pentanal 在 titanium(IV) isopropylate 、 正丁基锂 、 四甲基乙二胺 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 4.0h， 生成 <3R,4S,5R,6R<2S-(2-tetrahydropyranyl)oxy>>-1-<<(tert-butyldiphenyl)silyl>oxy>-8-<(N,N-diisopropyl)carbamate>-5-hydroxy-4-methyl-6-<2-<(2-tetrahydropyranyl)oxy>ethyl>-3-<<(triisopropyl)silyl>oxy>oct-7-ene 、 <3R,4S,5R,6R<2R-(2-tetrahydropyranyl)oxy>>-1-<<(tert-butyldiphenyl)silyl>oxy>-8-<(N,N-diisopropyl)carbamate>-5-hydroxy-4-methyl-6-<2-<(2-tetrahydropyranyl)oxy>ethyl>-3-<<(triisopropyl)silyl>oxy>oct-7-ene 、 <3R,4S,5S,6S<2S-(2-tetrahydropyranyl)oxy>>-1-<<(tert-butyldiphenyl)silyl>oxy>-8-<(N,N-diisopropyl)carbamate>-5-hydroxy-4-methyl-6-<2-<(2-tetrahydropyranyl)oxy>ethyl>-3-<<(triisopropyl)silyl>oxy>oct-7-ene 、 <3R,4S,5S,6S<2R-(2-tetrahydropyranyl)oxy>>-1-<<(tert-butyldiphenyl)silyl>oxy>-8-<(N,N-diisopropyl)carbamate>-5-hydroxy-4-methyl-6-<2-<(2-tetrahydropyranyl)oxy>ethyl>-3-<<(triisopropyl)silyl>oxy>oct-7-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
• 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 、 臭氧 、 (-)-B-甲氧基二异松莰基硼烷 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 二氯甲烷 为溶剂， 反应 6.5h， 生成 (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

文献信息

• Allyltitanates in Stereospecific Additions to Chiral δ-Lactol:  Efficient Enantioselective Route to a Potential Precursor of the C1−C9 Portion of Tylonolide
  作者：Isabelle Berque、Patrick Le Ménez、Patrick Razon、Jacqueline Mahuteau、Jean-Pierre Férézou、Ange Pancrazi、Janick Ardisson、Jean-Daniel Brion

  DOI：10.1021/jo9807722

  日期：1999.1.1

  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).