4-{[(tert-butyldiphenylsilyl)oxy]methyl}-2(E),4(Z)-hexadienal | 146983-23-5

• 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: 4-{[(tert-butyldiphenylsilyl)oxy]methyl}-2(E),4(Z)-hexadienal
• 英文别名: (2E,4Z)-4-[[tert-butyl(diphenyl)silyl]oxymethyl]hexa-2,4-dienal
• CAS: 146983-23-5
• 化学式: C₂₃H₂₈O₂Si
• 分子量: 364.56
• InChiKey: INLFDZMMDNIBGP-FRORLSQCSA-N

物化性质

• 沸点：
  452.0±45.0 °C(Predicted)
• 密度：
  1.02±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.26
• 重原子数：
  26.0
• 可旋转键数：
  7.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  26.3
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  4-{[(tert-butyldiphenylsilyl)oxy]methyl}-2(E),4(Z)-hexadienal 在 2,6-二叔丁基-4-甲基苯酚 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 三氯乙烯 为溶剂， 反应 16.0h， 生成 (E)-3-[9-(tert-Butyl-diphenyl-silanyloxymethyl)-2-cyclohexyl-10-methyl-4-oxo-1,3-dioxa-spiro[4.5]dec-8-en-7-yl]-2-methyl-acrylic acid ethyl ester
  参考文献：
  名称：

  Kijanolide上半部分的非对映选择性合成

  摘要：

  描述了焦亚醇胺的上半部分（4）的高度非对映选择性的合成。关键步骤是三烯6和手性亲二烯体6的exo和非对映体选择性Diels-Alder反应。

  DOI：

  10.1016/s0040-4039(00)70684-8
• 作为产物：
  描述：

  methyl (2E)-2-(hydroxymethyl)-2-butenoate 在 咪唑 、 manganese(IV) oxide 、 二异丁基氢化铝 作用下， 以 乙醚 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 生成 4-{[(tert-butyldiphenylsilyl)oxy]methyl}-2(E),4(Z)-hexadienal
  参考文献：
  名称：

  Kijanolide上半部分的非对映选择性合成

  摘要：

  描述了焦亚醇胺的上半部分（4）的高度非对映选择性的合成。关键步骤是三烯6和手性亲二烯体6的exo和非对映体选择性Diels-Alder反应。

  DOI：

  10.1016/s0040-4039(00)70684-8

文献信息

• Enantioselective synthesis of the top half of chlorothricolide
  作者：William R. Roush、Richard J. Sciotti

  DOI：10.1016/s0040-4039(00)61260-1

  日期：1992.8

  Highly enantio- and diastereoselective syntheses of spirotetronates 4 and 5 corresponding to the top half of chlorothricolide are described.

  描述了对应于氯环硫内酯上半部分的螺酮酸酯4和5的高度对映体和非对映体选择性合成。
• Studies on the Synthesis of Chlorothricolide:  Diastereo- and Enantioselective Syntheses of Model Top-Half Spirotetronate Units
  作者：William R. Roush、Richard J. Sciotti

  DOI：10.1021/jo980379w

  日期：1998.8.1

  Highly enantio- and diastereoselective syntheses of spirotetronates 9 and 10, corresponding to the top-half fragment of chlorothricolide, are described. Key steps in these syntheses are the Diels-Alder reactions of trienes 11 and 12 with the chiral dienophile (R)-6 that provide cycloadducts 18 and 38 with remarkably high stereoselectivity. These reactions exhibit exquisite regioselectivity for addition across the trisubstituted C(18)-C(21) diene unit; they also proceed with remarkable orientational control of the dienophile with respect to the C(18)-C(21) diene, as well as with excellent exo diastereofacial selectivity on the part of the chiral dienophile, (R)-6. Results are presented indicating that it is not necessary to control the stereochemistry of the C(20)-C(21) trisubstituted olefin of the triene precursors, as this unit :readily isomerizes under the conditions of the Diels-Alder reaction. Remarkably, the seemingly unreactive (E,E,E)-triene isomers (E,E,E)-11 and (E,E,E)-12 can be used as the starting material for the Diels-Alder reactions, and the desired exo-cycloadducts 18 and 38 are still obtained in good yield, without products of competitive Diels-Alder reactions of the disubstituted C(16)-C(19) dienes being observed.
• A highly diastereo- and enantioselective synthesis of the top half of kijanolide
  作者：William R. Roush、Bradley B. Brown

  DOI：10.1021/jo00060a035

  日期：1993.4

  A highly diastereo- and enantioselective synthesis of spirotetronate 4 corresponding to the top half of kijanolide is reported. This synthesis features the novel exo-selective Diels-Alder reaction of triene 6 and the chiral, nonracemic dienophiles (R)-7 and (R)-8. The reaction of 6 and (R)-7 produced a mixture of the desired exo cycloadduct 28, the unexpected exo diastereofacial isomer 29, and a minor amount of the endo cycloadduct 30. However, the Diels-Alder reaction of 6 and dienophile (R)-8 with the more sterically demanding tert-butyl substituent provided a 13-14:1 mixture of exo cycloadduct 38 and endo isomer 39; the exo diastereofacial isomer corresponding to 29 was not observed. Elaboration of 28 and 38 to spirotetronate 4 proceeded by way of the Dieckmann cyclization of alpha-acetoxy ester 5.
• ROUSH, WILLIAM R.;BROWN, BRADLEY B., TETRAHEDRON LETT., 30,(1989) N2, C. 7309-7312
  作者：ROUSH, WILLIAM R.、BROWN, BRADLEY B.

  DOI：——

  日期：——