2-bromo<3.3.0>bicyclooct-2-ene | 105231-21-8

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 乙烯基卤化物
• 英文名称: 2-bromo<3.3.0>bicyclooct-2-ene
• 英文别名: 2-bromobicyclo<3.3.0>oct-2-ene；(3aS,6aS)-6-bromo-1,2,3,3a,4,6a-hexahydropentalene
• CAS: 105231-21-8；119379-54-3
• 化学式: C₈H₁₁Br
• 分子量: 187.079
• InChiKey: HCJOJQPYFZJJMJ-BQBZGAKWSA-N

物化性质

• 沸点：
  90-92 °C(Press: 16 Torr)
• 密度：
  1.454±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.09
• 重原子数：
  9.0
• 可旋转键数：
  0.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  2-bromo<3.3.0>bicyclooct-2-ene 、 7,7-dimethoxybicyclo<2.2.1>hept-2-en-5-one 生成 (3aS,5aS,5bS,8aS,9aS,9bR)-3,3-Dimethoxy-3,3a,4,5a,5b,6,7,8,8a,9,9a,9b-dodecahydro-cyclopenta[b]-as-indacen-5-one
  参考文献：
  名称：

  Molecular recognition during 1,2-addition of chiral vinyl organometallics to chiral .beta.,.gamma.-unsaturated ketones. Case studies of three 7,7-disubstituted 2-norbornenones. Part 5

  摘要：

  DOI：

  10.1021/ja00211a031
• 作为产物：
  描述：

  tosylhydrazone of cis-bicyclo<3.3.0>octan-2-one 在 正丁基锂 、 溴化氰 、 四甲基乙二胺 作用下， 生成 2-bromo<3.3.0>bicyclooct-2-ene
  参考文献：
  名称：

  Molecular recognition during 1,2-addition of chiral vinyl organometallics to chiral .beta.,.gamma.-unsaturated ketones. Case studies of three 7,7-disubstituted 2-norbornenones. Part 5

  摘要：

  DOI：

  10.1021/ja00211a031

文献信息

• 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.
• Paquette, Leo A.; DeRussy, Donald T.; Vandenheste, Thierry, Journal of the American Chemical Society, 1990, vol. 112, # 14, p. 5562 - 5573
  作者：Paquette, Leo A.、DeRussy, Donald T.、Vandenheste, Thierry、Rogers, Robin D.

  DOI：——

  日期：——
• Probe of the Stereochemically Determining Step in Squarate Ester Cascades. Proof that Helical Equilibration within the Octatetraene Intermediate Is Responsible and Definition of Steric Control Elements
  作者：Leo A. Paquette、Ashton T. Hamme、Lung Huang Kuo、Julien Doyon、Rüdiger Kreuzholz

  DOI：10.1021/ja9632163

  日期：1997.2.1

  The stereoselectivity associated with the coaddition of a chiral and an achiral cycloalkenyl anion to a squarate ester has been examined. The selective formation of polycyclic ketones is observed in all cases, although dual protonation at both of the available enolate sites in their penultimate cyclooctatrienyl dianion precursors was sometimes noted. Proof that the stereoselection was the result of interconversion between a pair of helical octateraene intermediates, with resultant erosion of original stereogenicity, was established by isolation of diastereomeric monoadducts and separate submission of these hydroxy cyclobutenones to the original reaction conditions. The final stages of the cascade proceed via the lower energy transition state option where nonbonded steric effects are skirted as much as possible. These features are coordinated with subsequent stereocontrolled trans/annular aldol reactions during the quenching process. The adherence to these mechanistic guidelines is so all-encompassing that product sterochemistry can be reliably predicted from the outset.
• Doubly diastereoselective nucleophilic additions to a bicyclic β,γ-unsaturated ketone possessing a conformationally mobile double bond
  作者：Leo A. Paquette、Keith S. Learn、Jeffrey L. Romine

  DOI：10.1016/s0040-4020(01)87678-x

  日期：1987.1
• Model for diastereomer differentiation during 1,2-addition of chrial (racemic) cyclopentenyl organometallics to [4.2.0] bicyclic enones carrying exocyclic .beta.,.gamma.-double bonds
  作者：Leo A. Paquette、Donald T. DeRussy、Judith C. Gallucci

  DOI：10.1021/jo00271a009

  日期：1989.5