3,3-Dimethylbicyclo<2.2.2>oct-5-en-2-on | 53658-78-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3,3-Dimethylbicyclo<2.2.2>oct-5-en-2-on
• 英文别名: 3,3-Dimethylbicyclo<2.2.2>oct-5-en-2-one；α,α-Dimethyl-bicyclo<2,2,2>octanon；3,3-Dimethylbicyclo[2.2.2]oct-5-en-2-on；3,3-dimethylbicyclo[2.2.2]oct-5-en-2-one
• CAS: 53658-78-9
• 化学式: C₁₀H₁₄O
• 分子量: 150.221
• InChiKey: JFOQQZUPZVECQZ-UHFFFAOYSA-N

物化性质

• 沸点：
  215.7±9.0 °C(Predicted)
• 密度：
  0.993±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  3,3-Dimethylbicyclo<2.2.2>oct-5-en-2-on 在 18-冠醚-6 、 碘 、 叔丁基锂 、 potassium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 25.25h， 生成 (4aR*,6aS*,6bS*,8aS*,9aS*,9bR*)-3,4,4a,5,6a,6b,7,8,8a,9,9a,9b-Dodecahydro-5,5-dimethyl-6H-cyclobuta<3,4>cyclopenta<1,2-a>naphthalen-6-one
  参考文献：
  名称：

  Diastereoselectivities Associated with the 1,2-Addition of Chiral (Racemic) Cyclopentenyl Organometallics to Bicyclo[2.2.2]octenones

  摘要：

  The levels of diastereoselection attainable during condensation of the bicyclo[2.2.2]octenones 5-7 with organometallics derived from a selection of the vinyl bromides 8-12 have been determined. The 1,2-additions involving 6 exhibit excellent molecular recognition (>98:2) during syn (endo) addition to the carbonyl group. The diastereoselectivities associated with the capture of 5 and 7 are lower and more variable, although still respectable in several examples. In all cases, the dominant product is the alcohol in which the C-5 substituent on the nucleophilic subunit is beta-oriented. The structural assignments to the numerous alcohols follow from correlations of olefinic carbon chemical shifts, X-ray crystallography in selected examples, and anionic oxy-Cope rearrangement to generate polycyclic ketones whose stereochemical features were defined by NMR methods. The findings provide insight into the transition State geometries adopted in the course of these reactions. The model which has been formulated is consistent with the greater discriminatory power of 6 and conforms closely to earlier proposals for related reactions.

  DOI：

  10.1021/jo00087a017
• 作为产物：
  描述：

  双环[2.2.2]癸烷-2-烯-5-酮 、 碘甲烷 在 sodium hexamethyldisilazane 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 以72%的产率得到3,3-Dimethylbicyclo<2.2.2>oct-5-en-2-on
  参考文献：
  名称：

  Diastereoselectivities Associated with the 1,2-Addition of Chiral (Racemic) Cyclopentenyl Organometallics to Bicyclo[2.2.2]octenones

  摘要：

  The levels of diastereoselection attainable during condensation of the bicyclo[2.2.2]octenones 5-7 with organometallics derived from a selection of the vinyl bromides 8-12 have been determined. The 1,2-additions involving 6 exhibit excellent molecular recognition (>98:2) during syn (endo) addition to the carbonyl group. The diastereoselectivities associated with the capture of 5 and 7 are lower and more variable, although still respectable in several examples. In all cases, the dominant product is the alcohol in which the C-5 substituent on the nucleophilic subunit is beta-oriented. The structural assignments to the numerous alcohols follow from correlations of olefinic carbon chemical shifts, X-ray crystallography in selected examples, and anionic oxy-Cope rearrangement to generate polycyclic ketones whose stereochemical features were defined by NMR methods. The findings provide insight into the transition State geometries adopted in the course of these reactions. The model which has been formulated is consistent with the greater discriminatory power of 6 and conforms closely to earlier proposals for related reactions.

  DOI：

  10.1021/jo00087a017

文献信息

• Buchbauer, Gerhard; Spreitzer, Helmut; Kotlan, Ulla, Zeitschrift fur Naturforschung, B: Chemical Sciences, 1991, vol. 46, # 9, p. 1272 - 1274
  作者：Buchbauer, Gerhard、Spreitzer, Helmut、Kotlan, Ulla

  DOI：——

  日期：——
• Patel, Vijay; Stothers, J. B., Canadian Journal of Chemistry, 1980, vol. 58, p. 2728 - 2730
  作者：Patel, Vijay、Stothers, J. B.

  DOI：——

  日期：——
• PATEL V.; STOTHERS J. B., CAN. J. CHEM., 1980, 58, NO 23, 2728-2730
  作者：PATEL V.、 STOTHERS J. B.

  DOI：——

  日期：——
• US3967629A
  申请人：——

  公开号：US3967629A

  公开（公告）日：1976-07-06
• Diastereoselectivities Associated with the 1,2-Addition of Chiral (Racemic) Cyclopentenyl Organometallics to Bicyclo[2.2.2]octenones
  作者：Julien Doyon、Wei He、Leo A. Paquette

  DOI：10.1021/jo00087a017

  日期：1994.4

  The levels of diastereoselection attainable during condensation of the bicyclo[2.2.2]octenones 5-7 with organometallics derived from a selection of the vinyl bromides 8-12 have been determined. The 1,2-additions involving 6 exhibit excellent molecular recognition (>98:2) during syn (endo) addition to the carbonyl group. The diastereoselectivities associated with the capture of 5 and 7 are lower and more variable, although still respectable in several examples. In all cases, the dominant product is the alcohol in which the C-5 substituent on the nucleophilic subunit is beta-oriented. The structural assignments to the numerous alcohols follow from correlations of olefinic carbon chemical shifts, X-ray crystallography in selected examples, and anionic oxy-Cope rearrangement to generate polycyclic ketones whose stereochemical features were defined by NMR methods. The findings provide insight into the transition State geometries adopted in the course of these reactions. The model which has been formulated is consistent with the greater discriminatory power of 6 and conforms closely to earlier proposals for related reactions.