(2E,8Z)-(4S,5S)-5-(Triisopropylsiloxy)-4,8-dimethyl-9-<<(p-methoxybenzyl)oxy>methyl>-10-(methoxymethoxy)-2,8-decadienol | 171625-34-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2E,8Z)-(4S,5S)-5-(Triisopropylsiloxy)-4,8-dimethyl-9-<<(p-methoxybenzyl)oxy>methyl>-10-(methoxymethoxy)-2,8-decadienol
• 英文别名: (2E,4S,5S,8Z)-9-(methoxymethoxymethyl)-10-[(4-methoxyphenyl)methoxy]-4,8-dimethyl-5-tri(propan-2-yl)silyloxydeca-2,8-dien-1-ol
• CAS: 171625-34-6
• 化学式: C₃₂H₅₆O₆Si
• 分子量: 564.879
• InChiKey: BPBMPZUXRIZNBI-DBTVPBRISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.67
• 重原子数：
  39
• 可旋转键数：
  20
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  66.4
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (2E,8Z)-(4S,5S)-5-(Triisopropylsiloxy)-4,8-dimethyl-9-<<(p-methoxybenzyl)oxy>methyl>-10-(methoxymethoxy)-2,8-decadienol 在 2,4,6-三甲基吡啶 、 盐酸 、 正丁基锂 、 氯磺酰异氰酸酯 、 草酰氯 、 18-冠醚-6 、 六氯丙酮 、 双(三甲基硅烷基)氨基钾 、 sodium hydride 、 二异丁基氢化铝 、 caesium carbonate 、 二甲基亚砜 、 甲基磺酰氯 、 N,N-二异丙基乙胺 、 三苯基膦 、 2,3-二氯-5,6-二氰基-1,4-苯醌 、 lithium chloride 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 异丙醇 、 丙酮 为溶剂， 反应 28.41h， 生成 (1E,7E,9Z)-(5S,6S)-5-(Triisopropylsiloxy)-1-(hydroxymethyl)-2,6-dimethyl-1,7,9-cyclopentadecatrien-13-one
  参考文献：
  名称：

  Transannular Diels-Alder/Intramolecular Aldol Tandem Reaction as a Stereocontrolled Route to (+)-Aphidicolin and its Isosteric C8-Epimer1

  摘要：

  The trans,syn,cis A.B.C.[6.6.7] tricyclic subunit of aphidicolin could be derived from the transannular Diels-Alder (TADA) reaction of a trans,cis,cis (TCC) cyclopentadecatriene. On the other hand, a trans,trans,cis (TTC) isomeric cyclopentadecatriene could lead to the trans,syn,trans tricyclic skeleton of aphidicolin's C8-epimer. Interestingly, semiempirical calculations have shown the latter to be isosteric with aphidicolin in respect to the four hydroxyl groups. The required TCC and TTC 15-membered macrocyclic trienes 46 and 59 were synthesized using modern methods of acyclic stereoselection such as an organocopper-based difunctionalization reaction, Evans' asymmetric aldol methodology and Wittig-Horner-Wadsworth reactions. At the end, an efficient macrocyclization protocol served in achieving the synthesis of the desired optically active precursors 46 and 59. Whereas TCC substrate 46 failed to realize a TADA cycloaddition for steric and conformational reasons, TTC cyclopentadecatrienal 59 led to a stereospecific TADA/aldol tandem reaction. In the first reported example of such a transformation, macrocycle 59 was thermolyzed (toluene, sealed tube, 210 degrees C, 18 h) in a single operation into tetracyclic product 61 containing six new stereogenic centers. Mechanistic considerations of this impressive conversion along with transition-state modeling are also presented. Further transformations of compound 61 culminating in stereospecific functionalization at C16 were performed by making use of an hydroxyl-directed epoxidation reaction leading to the advanced intermediate 67. Thus, this exploratory work demonstrates the value of a TADA/aldol route for the synthesis of the titled compounds and analogs thereof.

  DOI：

  10.1021/jo00129a021
• 作为产物：
  描述：

  (2E/Z,8Z)-(4S,5S)-Methyl 5-(triisopropylsiloxy)-4,8-dimethyl-9-<<(p-methoxybenzyl)oxy>methyl>-10-(methoxymethoxy)-2,8-decadienoate 在 二异丁基氢化铝 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 1.0h， 以99%的产率得到(2E,8Z)-(4S,5S)-5-(Triisopropylsiloxy)-4,8-dimethyl-9-<<(p-methoxybenzyl)oxy>methyl>-10-(methoxymethoxy)-2,8-decadienol
  参考文献：
  名称：

  Transannular Diels-Alder/Intramolecular Aldol Tandem Reaction as a Stereocontrolled Route to (+)-Aphidicolin and its Isosteric C8-Epimer1

  摘要：

  The trans,syn,cis A.B.C.[6.6.7] tricyclic subunit of aphidicolin could be derived from the transannular Diels-Alder (TADA) reaction of a trans,cis,cis (TCC) cyclopentadecatriene. On the other hand, a trans,trans,cis (TTC) isomeric cyclopentadecatriene could lead to the trans,syn,trans tricyclic skeleton of aphidicolin's C8-epimer. Interestingly, semiempirical calculations have shown the latter to be isosteric with aphidicolin in respect to the four hydroxyl groups. The required TCC and TTC 15-membered macrocyclic trienes 46 and 59 were synthesized using modern methods of acyclic stereoselection such as an organocopper-based difunctionalization reaction, Evans' asymmetric aldol methodology and Wittig-Horner-Wadsworth reactions. At the end, an efficient macrocyclization protocol served in achieving the synthesis of the desired optically active precursors 46 and 59. Whereas TCC substrate 46 failed to realize a TADA cycloaddition for steric and conformational reasons, TTC cyclopentadecatrienal 59 led to a stereospecific TADA/aldol tandem reaction. In the first reported example of such a transformation, macrocycle 59 was thermolyzed (toluene, sealed tube, 210 degrees C, 18 h) in a single operation into tetracyclic product 61 containing six new stereogenic centers. Mechanistic considerations of this impressive conversion along with transition-state modeling are also presented. Further transformations of compound 61 culminating in stereospecific functionalization at C16 were performed by making use of an hydroxyl-directed epoxidation reaction leading to the advanced intermediate 67. Thus, this exploratory work demonstrates the value of a TADA/aldol route for the synthesis of the titled compounds and analogs thereof.

  DOI：

  10.1021/jo00129a021

文献信息

• Transannular Diels-Alder/Intramolecular Aldol Tandem Reaction as a Stereocontrolled Route to (+)-Aphidicolin and its Isosteric C8-Epimer1
  作者：Dennis G. Hall、Pierre Deslongchamps

  DOI：10.1021/jo00129a021

  日期：1995.12

  The trans,syn,cis A.B.C.[6.6.7] tricyclic subunit of aphidicolin could be derived from the transannular Diels-Alder (TADA) reaction of a trans,cis,cis (TCC) cyclopentadecatriene. On the other hand, a trans,trans,cis (TTC) isomeric cyclopentadecatriene could lead to the trans,syn,trans tricyclic skeleton of aphidicolin's C8-epimer. Interestingly, semiempirical calculations have shown the latter to be isosteric with aphidicolin in respect to the four hydroxyl groups. The required TCC and TTC 15-membered macrocyclic trienes 46 and 59 were synthesized using modern methods of acyclic stereoselection such as an organocopper-based difunctionalization reaction, Evans' asymmetric aldol methodology and Wittig-Horner-Wadsworth reactions. At the end, an efficient macrocyclization protocol served in achieving the synthesis of the desired optically active precursors 46 and 59. Whereas TCC substrate 46 failed to realize a TADA cycloaddition for steric and conformational reasons, TTC cyclopentadecatrienal 59 led to a stereospecific TADA/aldol tandem reaction. In the first reported example of such a transformation, macrocycle 59 was thermolyzed (toluene, sealed tube, 210 degrees C, 18 h) in a single operation into tetracyclic product 61 containing six new stereogenic centers. Mechanistic considerations of this impressive conversion along with transition-state modeling are also presented. Further transformations of compound 61 culminating in stereospecific functionalization at C16 were performed by making use of an hydroxyl-directed epoxidation reaction leading to the advanced intermediate 67. Thus, this exploratory work demonstrates the value of a TADA/aldol route for the synthesis of the titled compounds and analogs thereof.