methyl (1S,2R,5S)-4-<<(tert-butyldiphenylsilyl)oxy>methyl>-1-hydroxy-5-methyl-2-<2'-methyl-3'-<(tert-butyldimethylsilyl)oxy>-1'(E)-propen-1'-yl>-3-cyclohexene-1-carboxylate | 146983-28-0

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: methyl (1S,2R,5S)-4-<<(tert-butyldiphenylsilyl)oxy>methyl>-1-hydroxy-5-methyl-2-<2'-methyl-3'-<(tert-butyldimethylsilyl)oxy>-1'(E)-propen-1'-yl>-3-cyclohexene-1-carboxylate
• 英文别名: methyl (1S,2R,5S)-4-{[(tert-butyldiphenylsilyl)oxy]methyl}-1-hydroxy-5-methyl-2-{2'-methyl-3'-[(tert-butyldimethylsilyl)oxy]-1'(E)-propen-1'-yl}-3-cyclohexene-1-carboxylate；methyl (1S,2S,5S)-2-[(E)-3-[tert-butyl(dimethyl)silyl]oxy-2-methylprop-1-enyl]-4-[[tert-butyl(diphenyl)silyl]oxymethyl]-1-hydroxy-5-methylcyclohex-3-ene-1-carboxylate
• CAS: 146983-28-0
• 化学式: C₃₆H₅₄O₅Si₂
• 分子量: 622.993
• InChiKey: YGEUVVGEUFQGOX-WGXUFQTESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.02
• 重原子数：
  43
• 可旋转键数：
  13
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  65
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl (1S,2R,5S)-4-<<(tert-butyldiphenylsilyl)oxy>methyl>-1-hydroxy-5-methyl-2-<2'-methyl-3'-<(tert-butyldimethylsilyl)oxy>-1'(E)-propen-1'-yl>-3-cyclohexene-1-carboxylate 在 六甲基磷酰三胺 、 4-二甲氨基吡啶 、 三乙胺 、 lithium hexamethyldisilazane 作用下， 以 二氯甲烷 为溶剂， 反应 17.25h， 生成 (5S,6R,9S)-8-<<(tert-butyldiphenylsilyl)oxy>methyl>-4-(methoxymethoxy)-6-<2'-methyl-3'-<(tert-butyldimethylsilyl)oxy>-1'(E)-propen-1'-yl>-1-oxaspiro<4.5>deca-3,7-dien-2-one
  参考文献：
  名称：

  A highly diastereo- and enantioselective synthesis of the top half of kijanolide

  摘要：

  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.

  DOI：

  10.1021/jo00060a035
• 作为产物：
  描述：

  3-羟基-2-亚甲基丁酸甲酯 在 咪唑 、 manganese(IV) oxide 、 N-溴代丁二酰亚胺(NBS) 、 草酰氯 、 2,3-二巯基丁二酸 、 2,6-二叔丁基-4-甲基苯酚 、 sodium acetate 、 二异丁基氢化铝 、 potassium carbonate 、 二甲基亚砜 、 三乙胺 、 lithium hexamethyldisilazane 作用下， 以 乙醚 、 正己烷 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 216.25h， 生成 methyl (1S,2R,5S)-4-<<(tert-butyldiphenylsilyl)oxy>methyl>-1-hydroxy-5-methyl-2-<2'-methyl-3'-<(tert-butyldimethylsilyl)oxy>-1'(E)-propen-1'-yl>-3-cyclohexene-1-carboxylate
  参考文献：
  名称：

  A highly diastereo- and enantioselective synthesis of the top half of kijanolide

  摘要：

  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.

  DOI：

  10.1021/jo00060a035

文献信息

• 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.