4-bromo-endo-tricyclo<5.2.1.0^2,6>deca-4,8-dien-3-one

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-bromo-endo-tricyclo<5.2.1.0^2,6>deca-4,8-dien-3-one
• 英文别名: 2-Brom-3a,4,7,7a-tetrahydro-4,7-methano-endo-indenon-(1)；4-bromo-endo-tricyclo[5.2.1.0^2,6]deca-4,8-dien-3-one；(1S,2R,6S,7R)-4-bromotricyclo[5.2.1.02,6]deca-4,8-dien-3-one
• 化学式: C₁₀H₉BrO
• 分子量: 225.085
• InChiKey: ARURZIWRHKJDMP-VOQBNFLRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 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：

  4-bromo-endo-tricyclo<5.2.1.0^2,6>deca-4,8-dien-3-one 以 乙酸乙酯 为溶剂， 生成 5-Brom-pentacyclo<5.3.0.0^2,5.0^3,9.0^4,8>decanon-6
  参考文献：
  名称：

  Synthesis of pentacyclo[4.3.0.02,5.02,8.04,7]nonane (homocubane) and some of its derivatives

  摘要：

  DOI：

  10.1021/jo01268a030
• 作为产物：
  描述：

  endo-tricyclo[5.2.1.0(2,6)]deca-4,8-dien-3-one 在 溴 、 三乙胺 作用下， 以 四氯化碳 为溶剂， 以80%的产率得到4-bromo-endo-tricyclo<5.2.1.0^2,6>deca-4,8-dien-3-one
  参考文献：
  名称：

  Halogen addition to - and -tricyclo[5.2.1.02,6]deca-4,8-dien-3-ones

  摘要：

  The reactions of endo- and exo-tricyclodecadienones 2a-c and 3a-c with bromine and iodine are described. The chemo- and regioselectivity of these additions depend on the nature of both reagent and substrate and are explained in terms of the configuration of the tricyclic compounds and the general mechanism for electrophilic halogenation. From a synthetic point of view only the bromination of endo-tricyclodecadienone 2a is useful. Other reactions fail (2a-c with I-2), result in addition to the norbornene double bond (3a-c with I-2) or give rise to complex mixtures (2b-c and 3a-c with Br-2).

  DOI：

  10.1016/s0040-4020(01)81818-4

文献信息

• Reversal of facial selectivity in complex Diels–Alder reactions
  作者：Jacques-Alexis Funel、Louis Ricard、Joëlle Prunet

  DOI：10.1039/b509041e

  日期：——

  A complex Diels-Alder reaction between a semi-cyclic diene with allylic silyloxy substituents and a bromo enone presented an unusual diastereoselectivity: attack of the diene occured on its more hindered face, and this reversal of selectivity was shown to be induced by the presence of a bromo substituent in the dienophile.

  具有烯丙基甲硅烷基氧基取代基的半环二烯与溴烯酮之间的复杂Diels-Alder反应表现出不同寻常的非对映选择性：二烯的进攻发生在其更受阻的面上，并且这种选择性的逆转被证明是由于存在亲双烯体中的溴取代基。
• 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.
• WO2023/285883
  申请人：——

  公开号：——

  公开（公告）日：——
• Halogen addition to - and -tricyclo[5.2.1.02,6]deca-4,8-dien-3-ones
  作者：Paul P.M.A. Dols、Antonius J.H. Klunder、Binne Zwanenburg

  DOI：10.1016/s0040-4020(01)81818-4

  日期：1993.1

  The reactions of endo- and exo-tricyclodecadienones 2a-c and 3a-c with bromine and iodine are described. The chemo- and regioselectivity of these additions depend on the nature of both reagent and substrate and are explained in terms of the configuration of the tricyclic compounds and the general mechanism for electrophilic halogenation. From a synthetic point of view only the bromination of endo-tricyclodecadienone 2a is useful. Other reactions fail (2a-c with I-2), result in addition to the norbornene double bond (3a-c with I-2) or give rise to complex mixtures (2b-c and 3a-c with Br-2).
• Synthesis of pentacyclo[4.3.0.02,5.02,8.04,7]nonane (homocubane) and some of its derivatives
  作者：George L. Dunn、Vincent J. DePasquo、John R. E. Hoover

  DOI：10.1021/jo01268a030

  日期：1968.4