(2R,5S,6R,9R)-2-tert-butyl-6-[(E)-7-[tert-butyl(dimethyl)silyl]oxyhept-1-enyl]-8-[[tert-butyl(diphenyl)silyl]oxymethyl]-9-methyl-1,3-dioxaspiro[4.5]dec-7-en-4-one | 144446-55-9

• 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: (2R,5S,6R,9R)-2-tert-butyl-6-[(E)-7-[tert-butyl(dimethyl)silyl]oxyhept-1-enyl]-8-[[tert-butyl(diphenyl)silyl]oxymethyl]-9-methyl-1,3-dioxaspiro[4.5]dec-7-en-4-one
• CAS: 144446-55-9
• 化学式: C₄₃H₆₆O₅Si₂
• 分子量: 719.165
• InChiKey: JLNBWEQAVVZONB-WVYYYNQJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.97
• 重原子数：
  50
• 可旋转键数：
  16
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  54
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (2R,5S,6R,9R)-2-tert-butyl-6-[(E)-7-[tert-butyl(dimethyl)silyl]oxyhept-1-enyl]-8-[[tert-butyl(diphenyl)silyl]oxymethyl]-9-methyl-1,3-dioxaspiro[4.5]dec-7-en-4-one 在 4-二甲氨基吡啶 、 potassium carbonate 、 N,N'-二环己基碳二亚胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 22.0h， 生成 methyl (1S,2R,5R)-2-[(E)-7-[tert-butyl(dimethyl)silyl]oxyhept-1-enyl]-4-[[tert-butyl(diphenyl)silyl]oxymethyl]-5-methyl-1-(2-phenylmethoxyacetyl)oxycyclohex-3-ene-1-carboxylate
  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：

  2-{[(tert-butyldiphenylsilyl)oxy]methyl}-2(E)-butenal 在 四(三苯基膦)钯 正丁基锂 、 2,6-二叔丁基-4-甲基苯酚 、 三乙胺 、 三苯基膦 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 三氯乙烯 、 水 为溶剂， 反应 2.5h， 生成 (2R,5S,6R,9R)-2-tert-butyl-6-[(E)-7-[tert-butyl(dimethyl)silyl]oxyhept-1-enyl]-8-[[tert-butyl(diphenyl)silyl]oxymethyl]-9-methyl-1,3-dioxaspiro[4.5]dec-7-en-4-one
  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

文献信息

• 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.