methyl (E)-3-[(2R,5S,6R,9R)-2-tert-butyl-8-[[tert-butyl(diphenyl)silyl]oxymethyl]-9-methyl-4-oxo-1,3-dioxaspiro[4.5]dec-7-en-6-yl]prop-2-enoate | 144446-48-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并呋喃
• 英文名称: methyl (E)-3-[(2R,5S,6R,9R)-2-tert-butyl-8-[[tert-butyl(diphenyl)silyl]oxymethyl]-9-methyl-4-oxo-1,3-dioxaspiro[4.5]dec-7-en-6-yl]prop-2-enoate
• CAS: 144446-48-0
• 化学式: C₃₄H₄₄O₆Si
• 分子量: 576.805
• InChiKey: XGJULYWRAQXTPN-IDICDCPBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.56
• 重原子数：
  41
• 可旋转键数：
  10
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  71.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl (E)-3-[(2R,5S,6R,9R)-2-tert-butyl-8-[[tert-butyl(diphenyl)silyl]oxymethyl]-9-methyl-4-oxo-1,3-dioxaspiro[4.5]dec-7-en-6-yl]prop-2-enoate 在 咪唑 、 4-二甲氨基吡啶 、 lithium aluminium tetrahydride 、 二异丁基氢化铝 、 三乙胺 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 14.25h， 生成 (S)-3,3,3-Trifluoro-2-methoxy-2-phenyl-propionic acid (1S,2R,5R)-2-[(E)-3-(tert-butyl-dimethyl-silanyloxy)-propenyl]-4-(tert-butyl-diphenyl-silanyloxymethyl)-1-hydroxy-5-methyl-cyclohex-3-enylmethyl ester
  参考文献：
  名称：

  Studies on the Synthesis of Chlorothricolide:  Diastereo- and Enantioselective Syntheses of Model Top-Half Spirotetronate Units

  摘要：

  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.

  DOI：

  10.1021/jo980379w
• 作为产物：
  描述：

  4-{[(tert-butyldiphenylsilyl)oxy]methyl}-2(E),4(Z)-hexadienal 在 2,6-二叔丁基-4-甲基苯酚 作用下， 以 二氯甲烷 、 三氯乙烯 为溶剂， 生成 methyl (E)-3-[(2R,5S,6R,9R)-2-tert-butyl-8-[[tert-butyl(diphenyl)silyl]oxymethyl]-9-methyl-4-oxo-1,3-dioxaspiro[4.5]dec-7-en-6-yl]prop-2-enoate
  参考文献：
  名称：

  对映选择性合成氯环内酯的上半部分

  摘要：

  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。

  DOI：

  10.1016/s0040-4039(00)61260-1