1-bromo-6-methoxy-cyclohexene | 145091-07-2

• 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: 1-bromo-6-methoxy-cyclohexene
• 英文别名: 1-bromo-6-methoxycyclohexene；2-Bromo-2-cyclohexen-1-YL methyl ether
• CAS: 145091-07-2
• 化学式: C₇H₁₁BrO
• 分子量: 191.068
• InChiKey: FPAXROPSIFIQFV-UHFFFAOYSA-N

物化性质

• 沸点：
  208.9±40.0 °C(Predicted)
• 密度：
  1.37±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-bromo-6-methoxy-cyclohexene 在 manganese(IV) oxide 、 正丁基锂 、 碘 、 锌 作用下， 以 乙酸乙酯 为溶剂， 反应 9.5h， 生成 2-<1-Carbo-tert-butoxyacetyl>-1-methoxy-2-cyclohexene
  参考文献：
  名称：

  Lavallee, Jean-Francois; Spino, Claude; Ruel, Rejean, Canadian Journal of Chemistry, 1992, vol. 70, # 5, p. 1406 - 1426

  摘要：

  DOI：
• 作为产物：
  描述：

  2-溴-2-环己烯-1-酮 在 sodium tetrahydroborate 、 cerium(III) chloride 、 双(三甲基硅烷基)氨基钾 作用下， 以 乙醇 为溶剂， 反应 10.0h， 生成 1-bromo-6-methoxy-cyclohexene
  参考文献：
  名称：

  Lavallee, Jean-Francois; Spino, Claude; Ruel, Rejean, Canadian Journal of Chemistry, 1992, vol. 70, # 5, p. 1406 - 1426

  摘要：

  DOI：

文献信息

• Delineating the possibilities for intramolecular interception of the squarate ester cascade through the use of metalated enecarbamates
  作者：Jinsung Tae、Leo A Paquette

  DOI：10.1139/v99-235

  日期：2000.6.1

  Highly functionalized and annulated 2,4-cyclooctadienones are formed in a stereoselective manner by sequential treatment of squarate esters with a lithiated enecarbamate (six-membered ring or larger) and a cycloalkenyl- or 1-alkenyllithium reagent. The mechanistic details of this multistep process are presented. Particular attention is drawn to the step that involves intramolecular nucleophilic attack by a proximal oxido anion at the carbamate carbonyl and results in redirection of the cascade. This step is thwarted when five-membered cyclic enecarbamates are employed because of the excessive buildup of ring strain in the associated transition state.Key words: squarate esters, enecarbamates, conrotatory ring opening, intramolecular acylation, alkenyllithium reagents.

  通过将方酸酯依次处理为锂化烯基氨甲酸酯（六元环或更大）和环烯基或1-烯基锂试剂，以立体选择性的方式形成高度官能化和环化的2,4-环辛二酮。介绍了这个多步反应的机理细节。特别关注涉及近端氧化阴离子对氨甲酸酯羰基的分子内亲核攻击步骤，该步骤导致级联重定向。当采用五元环的环烯基氨甲酸酯时，由于相关过渡态中环张力的过度积累，此步骤会受到阻碍。关键词：方酸酯，烯基氨甲酸酯，同构环开放，分子内酰化，烯基锂试剂。
• A New Tandem Route to Angular Tetraquinanes. Synthesis of the Waihoensene Ring System
  作者：Jens-Kerim Ergüden、Harold W. Moore

  DOI：10.1021/ol990023m

  日期：1999.8.1

  text] This paper describes a new tandem reaction sequence leading to angularly fused polyquinanes from squaric acid-derived bicyclo[6.3.0]-undecadienediones. Such compounds undergo a dual Michael addition. The enolate form in the first intermolecular addition undergoes the second intramolecular transannular addition to give the angular polyquinanes. A particularly interesting example is a catalytic transformation

  [公式：参见文本]本文描述了一种新的串联反应序列，该序列可从方酸衍生的双环[6.3.0]-十一碳二烯中产生角熔融的聚喹烷。这样的化合物经历双重迈克尔加成。第一次分子间加成中的烯醇化物形式经历第二次分子内环过环加成，得到角聚喹烷。一个特别有趣的例子是顺式13-甲基环环[10.3.0.0] pentadeca-4（5），12（13）-二烯-3,14-二酮的催化转化为（3R *，3aS *，5aR *，9aR *，11aR *）-3-甲基-1,2,3,5,5a，6，7,10,11,11a-十氢-4H-戊二烯[6a，1-c]茚-2,10-二酮，在天然产物waihoensene中发现的具有四环系统的化合物。讨论了这些反应的机理和合成范围。
• Realization of Complete Regiochemical Control during the Conversion of Squarate Esters into Complex Linear and Angular Polyquinanes. The Consequences of Incorporating a Leaving Group into One of the Alkenyllithium Reactants
  作者：Leo A. Paquette、Julien Doyon

  DOI：10.1021/jo962181m

  日期：1997.3.1

  A useful method is presented for controlling whether linear or angular triquinanes are formed during a reaction cascade initiated by the 2-fold addition of alkenyl anions to diisopropyl squarate, The key feature of the process involves the incorporation of a leaving group into one of the original nucleophilic reagents. Placement of the nucleofuge within a cyclic anion leads ultimately to formation of a linear product. Extracyclic and intracyclic options are possible, with preference given to the better leaving group when a competitive situation exists, When the leaving group is incorporated into an acyclic component, angular triquinanes result instead. Several other aspects of this impressive scaffolding scheme are detailed.
• Evaluation of Amino Substituents as Nucleofugal Controllers of Regioselectivity and as Chelate Modulators of Stereoselectivity in Squarate Ester Cascades
  作者：Leo A. Paquette、Lung Huang Kuo、Jinsung Tae

  DOI：10.1021/jo9722919

  日期：1998.3.1

  The tandem addition of an alkenyllithium reagent and a 2-lithioallylamine to squarate esters has been systematically examined. The effect of the sequencing of this twofold addition has been investigated. The extent to which the amino group is eliminated was found to be dependent on the structural features of the companion nucleophile. Also assessed was the comparative ease with which the amino and methoxy groups experience competitive beta-elimination from the highly reactive, medium-ring dianionic intermediates. Attempts were made to curtail the level of competing 1,4-addition, and success was achieved by increasing the effective size of the O-alkyl groups in the squarate ester. The highly stereocontrolled transformations described represent a notably direct means for producing highly fused polycyclic compounds, Mechanistic considerations sm rounding these reactions, which are characterized by an impressive enhancement of molecular scaffolding, are discussed.