(1S,3R,4S)-1-<(E)-2-<(2R,3S)-3-(benzyloxy)-2-<2-(tert-butyldimethylsilyloxy)ethyl>-3-oxetanyl>vinyl>-3-(methoxymethoxy)-7,7-dimethylbicyclo<2.2.1>-heptan-2-one | 220325-48-4

• 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: (1S,3R,4S)-1-<(E)-2-<(2R,3S)-3-(benzyloxy)-2-<2-(tert-butyldimethylsilyloxy)ethyl>-3-oxetanyl>vinyl>-3-(methoxymethoxy)-7,7-dimethylbicyclo<2.2.1>-heptan-2-one
• 英文别名: (1S,3R,4S)-1-[(E)-2-[(2R,3S)-2-[2-[tert-butyl(dimethyl)silyl]oxyethyl]-3-phenylmethoxyoxetan-3-yl]ethenyl]-3-(methoxymethoxy)-7,7-dimethylbicyclo[2.2.1]heptan-2-one
• CAS: 220325-48-4
• 化学式: C₃₁H₄₈O₆Si
• 分子量: 544.804
• InChiKey: UOVDTFBWYCTMET-GIHDDHJQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.3
• 重原子数：
  38
• 可旋转键数：
  13
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  63.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (1S,3R,4S)-1-<(E)-2-<(2R,3S)-3-(benzyloxy)-2-<2-(tert-butyldimethylsilyloxy)ethyl>-3-oxetanyl>vinyl>-3-(methoxymethoxy)-7,7-dimethylbicyclo<2.2.1>-heptan-2-one 在 lithium aluminium tetrahydride 、 18-冠醚-6 、 叔丁基锂 、 potassium hydride 作用下， 以 四氢呋喃 、 乙醚 、 正戊烷 为溶剂， 反应 3.5h， 生成 (E)-(1S,2R,3R,5S,6R)-6-{(2R,3S)-3-Benzyloxy-2-[2-(tert-butyl-dimethyl-silanyloxy)-ethyl]-oxetan-3-yl}-2-methoxymethoxy-5,11,11-trimethyl-bicyclo[6.2.1]undec-7-en-3-ol
  参考文献：
  名称：

  Reversible Charge-Accelerated Oxy-Cope Rearrangements

  摘要：

  An asymmetric synthesis of the oxetane-containing norbornanone 23 and its coupling to trans-1-propenyllithium to give 24 are reported, in tandem with the preparation of the related alcohols 28 and 30. All three divinyl carbinols undergo anionic oxy-Cope rearrangement very rapidly at low temperature. Quenching of 24(-)K(+) and 28(-)K(+) under these conditions with water or various aqueous salt solutions results in protonation of the alkoxides. If these reaction mixtures are poured instead onto cold (0 degrees C) silica gel, their sigmatropically related ketones are isolated in very good yield. Whereas the 24(-)K(+) <--(-->) 25(-)K(+) equilibrium pair is not reactive to molecular oxygen, 30(-)K(+) is directly converted into an a-hydroperoxy ketone under comparable conditions. These and additional observations are rationalized in the context of atropisomerism involving conversion of oxygen-up enolates, formed reversibly under kinetically controlled conditions, into their thermodynamically favored, more reactive oxygen-down conformers.

  DOI：

  10.1021/jo982002w
• 作为产物：
  描述：

  (3aR,5R,6R,6aR)-5-<2-(tert-butyldimethylsilyloxy)ethyl>-tetrahydro-6-<(E)-2-<(1S,2R,4R)-2-hydroxy-7,7-dimethylbicyclo<2.2.1>hept-1-yl>vinyl>-2,2-dimethylfuro<2,3-d>-1,3-dioxol-6-ol 在 sodium tetrahydroborate 、 四氯化钛 、 四丁基碘化铵 、 双(三甲基硅烷基)氨基钾 、 sodium hydride 、 戴斯-马丁氧化剂 、 2-[N,正双(三氟甲烷烷磺酰)氨基]-5-氯吡啶 、 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 11.25h， 生成 (1S,3R,4S)-1-<(E)-2-<(2R,3S)-3-(benzyloxy)-2-<2-(tert-butyldimethylsilyloxy)ethyl>-3-oxetanyl>vinyl>-3-(methoxymethoxy)-7,7-dimethylbicyclo<2.2.1>-heptan-2-one
  参考文献：
  名称：

  Reversible Charge-Accelerated Oxy-Cope Rearrangements

  摘要：

  An asymmetric synthesis of the oxetane-containing norbornanone 23 and its coupling to trans-1-propenyllithium to give 24 are reported, in tandem with the preparation of the related alcohols 28 and 30. All three divinyl carbinols undergo anionic oxy-Cope rearrangement very rapidly at low temperature. Quenching of 24(-)K(+) and 28(-)K(+) under these conditions with water or various aqueous salt solutions results in protonation of the alkoxides. If these reaction mixtures are poured instead onto cold (0 degrees C) silica gel, their sigmatropically related ketones are isolated in very good yield. Whereas the 24(-)K(+) <--(-->) 25(-)K(+) equilibrium pair is not reactive to molecular oxygen, 30(-)K(+) is directly converted into an a-hydroperoxy ketone under comparable conditions. These and additional observations are rationalized in the context of atropisomerism involving conversion of oxygen-up enolates, formed reversibly under kinetically controlled conditions, into their thermodynamically favored, more reactive oxygen-down conformers.

  DOI：

  10.1021/jo982002w

文献信息

• Reversible Charge-Accelerated Oxy-Cope Rearrangements
  作者：Hon-Chung Tsui、Leo A. Paquette

  DOI：10.1021/jo982002w

  日期：1998.12.1

  An asymmetric synthesis of the oxetane-containing norbornanone 23 and its coupling to trans-1-propenyllithium to give 24 are reported, in tandem with the preparation of the related alcohols 28 and 30. All three divinyl carbinols undergo anionic oxy-Cope rearrangement very rapidly at low temperature. Quenching of 24(-)K(+) and 28(-)K(+) under these conditions with water or various aqueous salt solutions results in protonation of the alkoxides. If these reaction mixtures are poured instead onto cold (0 degrees C) silica gel, their sigmatropically related ketones are isolated in very good yield. Whereas the 24(-)K(+) <--(-->) 25(-)K(+) equilibrium pair is not reactive to molecular oxygen, 30(-)K(+) is directly converted into an a-hydroperoxy ketone under comparable conditions. These and additional observations are rationalized in the context of atropisomerism involving conversion of oxygen-up enolates, formed reversibly under kinetically controlled conditions, into their thermodynamically favored, more reactive oxygen-down conformers.