1-phenylbicyclo<1.1.1>pentane | 134938-21-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1-phenylbicyclo<1.1.1>pentane
• 英文别名: 1-phenylbicyclo[1.1.1]pentane
• CAS: 134938-21-9
• 化学式: C₁₁H₁₂
• 分子量: 144.216
• InChiKey: QEWRLQJVHCDTOM-UHFFFAOYSA-N

物化性质

• 沸点：
  211.4±7.0 °C(Predicted)
• 密度：
  1.120±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  1-phenylbicyclo<1.1.1>pentane 在 1-溴-1-氯-2,2,2-三氟乙烷 、 叔丁基锂 、 N,N'-二环己基碳二亚胺 作用下， 以 正戊烷 为溶剂， 生成 1-bromo-3-phenylbicyclo<1.1.1>pentane
  参考文献：
  名称：

  Synthesis of Some Bridgehead-Bridgehead-Disubstituted Bicyclo[1.1.1]pentanes

  摘要：

  The synthesis of a wide variety of 1,3-disubstituted bicyclo[1.1.1]pentanes is described, with particular emphasis on the generation of a series of S-X-substituted bicyclo[1.1.1]pentyl bromides required for solvolytic studies. Functional group manipulation at the bridgehead was readily accomplished in the majority of cases by radical processes in some instances, transformations were effected via carbanionic-type intermediates.

  DOI：

  10.1021/jo00090a015
• 作为产物：
  描述：

  1-bromo-3-phenylbicyclo<1.1.1>pentane 在 偶氮二异丁腈 、 三正丁基氢锡 作用下， 反应 0.08h， 以73%的产率得到1-phenylbicyclo<1.1.1>pentane
  参考文献：
  名称：

  Experimental and calculated activation parameters for ring opening of the 1-bicyclo[1.1.1]pentyl radical: the effect of bridgehead substituents

  摘要：

  Ring opening of the 1-bicyclo[1.1.1]pentyl, 3-pentyl-1-bicyclo[1.1.1]pentyl, and 3-carbomethoxy-1-bicyclo[1.1.1]pentyl radicals has been studied by experiment and by molecular orbital theory. Our results indicate that the parent system 1a is extremely reluctant to ring open, with an energy barrier of at least 26 kcal mol-1. The ester- and phenyl-substituted radicals rearrange somewhat more readily, with barriers of about 25 and 21 kcal mol-1, respectively. This trend is also observed in the molecular orbital treatment of these processes. Previous reports that include radical rearrangements of this type must now be reconsidered in light of our new data.

  DOI：

  10.1021/jo00015a018

文献信息

• Nickel- and Palladium-Catalyzed Cross-Coupling Reactions at the Bridgehead of Bicyclo[1.1.1]pentane Derivatives - A Convenient Access to Liquid Crystalline Compounds Containing Bicyclo[1.1.1]pentane Moieties
  作者：Matthias Messner、Sergei I. Kozhushkov、Armin de Meijere

  DOI：10.1002/1099-0690(200004)2000:7<1137::aid-ejoc1137>3.0.co;2-2

  日期：2000.4

  Pd(PPh3)4, or PdCl2(dppf) catalysis to give a number of 1,3-disubstituted bicyclo[1.1.1]pentyl derivatives 17, 20, and 23, several of which exhibit liquid crystalline properties, in moderate to very good yields. The coupling products 20ca, 23ab, 23ae, 23ff, and 23fg have been further transformed to yield bicyclo[1.1.1]pentyl derivatives 32, 24ab, 24ae, 27ff, and 27fg, respectively, bearing alkynyl, cyano

  有机碘化物 7a-s 在 [1.1.1] 推进烷 (2) 上的自由基加成反应，然后是卤素-锂交换和与氯化锌的金属转移，以及将格利雅试剂添加到 2，提供了各种 3-取代双环[1.1.1]pentyl-1-magnesium (14) 和-zinc (19) 衍生物。后者在 NiCl2dppe、Pd(PPh3)4 或 PdCl2(dppf) 催化下与各种烯基、芳基和联芳基卤化物和三氟甲磺酸酯偶联，得到许多 1,3-二取代的双环 [1.1.1] 戊基衍生物 17 、20和23，其中一些表现出液晶性质，产率中等至非常好。偶联产物 20ca、23ab、23ae、23ff 和 23fg 已进一步转化为双环 [1.1.1] 戊基衍生物 32、24ab、24ae、27ff 和 27fg，分别带有炔基、氰基和/或烯基.
• Compounds and methods based on [1.1.1]propellane
  申请人：Michl; Josef

  公开号：US05405550A1

  公开（公告）日：1995-04-11

  Molecular bulding beams, liquid crystals, and surfactants in the form of compounds based on [1.1.1]propellane, including poly[1.1.1]propellanes. Molecular building beams having a telomeric or polymeric chain staff, and linking groups functionalized on one or both ends of the staff. A system for linking the beams to connecting units to construct molecular structures of various forms, such as whips, combs, scaffoldings, nets, or stars. Other broad aspects of the invention provide liquid crystals and surfactants. The liquid crystals include telomeric or polymeric compounds functionalized with flexible end groups, while the surfactant compounds are functionalized with surface active end groups. Methods of synthesizing the various compounds ar also provided.

  分子构建梁，液晶体和表面活性剂以基于[1.1.1]丙烷的化合物形式存在，包括聚[1.1.1]丙烷。分子构建梁具有端部或聚合链杆，以及在杆的一端或两端上功能化的连接基团。系统将梁连接到连接单元以构建各种形式的分子结构，例如鞭、梳子、脚手架、网或星形。发明的其他广泛方面提供液晶体和表面活性剂。液晶体包括功能化有柔性末端基团的端部或聚合化合物，而表面活性剂化合物则功能化有表面活性末端基团。还提供了合成各种化合物的方法。
• Skeletal Editing Approach to Bridge-Functionalized Bicyclo[1.1.1]pentanes from Azabicyclo[2.1.1]hexanes
  作者：Brandon A. Wright、Anastassia Matviitsuk、Michael J. Black、Pablo García-Reynaga、Luke E. Hanna、Aaron T. Herrmann、Michael K. Ameriks、Richmond Sarpong、Terry P. Lebold

  DOI：10.1021/jacs.3c02616

  日期：2023.5.24

  Azabicyclo[2.1.1]hexanes (aza-BCHs) and bicyclo[1.1.1]pentanes (BCPs) have emerged as attractive classes of sp3-rich cores for replacing flat, aromatic groups with metabolically resistant, three-dimensional frameworks in drug scaffolds. Strategies to directly convert, or “scaffold hop”, between these bioisosteric subclasses through single-atom skeletal editing would enable efficient interpolation within

  氮杂双环[2.1.1]己烷 (aza-BCH) 和双环[1.1.1]戊烷 (BCP) 已成为富含sp 3的有吸引力的核心类别，用于在药物中用耐代谢的三维框架取代扁平芳香基团脚手架。通过单原子骨架编辑在这些生物电子等排子类之间直接转换或“支架跳跃”的策略将能够在这个有价值的化学空间内进行有效的插值。在此，我们描述了一种通过脱氮骨架编辑在 aza-BCH 和 BCP 核心之间“支架跳跃”的策略。光化学[2+2]环加成用于制备多功能化的aza-BCH框架，与随后的脱氨基步骤相结合以提供桥功能化的BCP，目前很少有合成解决方案。模块化序列提供了对制药相关的各种特权桥式自行车的访问。
• Mechanistic studies of fluorodecarboxylation with xenon difluoride
  作者：Timothy B. Patrick、Sadegh Khazaeli、Sourena Nadji、Katy Hering-Smith、Dirk Reif

  DOI：10.1021/jo00055a026

  日期：1993.1

  The reaction of xenon difluoride with primary carboxylic acids involves a free-radical mechanism. Trifluoroacetic acid (1) decarboxylates in benzene to give (trifluoromethyl)benzene (2). 6-Hexenoic acid (3) produces a free radical in a radical clock reaction in which the k(abs) (25-degrees-C) for XeF2 Was determined as 1.1 X 10(6) M-1 s-1. The primary radical from hexanoic acid was spin-trapped to give ESR signals diagnostic for the alkyl radical. Secondary acids were shown to proceed through a trivalent intermediate, but its exact nature was not proven. The acid 6 gave a rearranged product (7) characteristic of carbocations, whereas the diacid 8 gave difluoro compounds without stereoselectivity. The tertiary bicyclic acids 13 and 15 gave products only from solvent hydrogen abstraction strongly indicative of free radicals.
• Experimental and theoretical study of substituent effects on3J(13C1-1H) coupling constants in 1-X-bicyclo[1.1.1]pentanes
  作者：Ernest W. Della、Ian J. Lochert、N�lida M. Peruchena、Gustavo A. Aucar、Rub�n H. Contreras

  DOI：10.1002/(sici)1099-1395(199603)9:3<168::aid-poc766>3.0.co;2-v

  日期：1996.3

  A series of 23 bridgehead-substituted bicyclo[1,1,1]pentanes were synthesized and the (3)J(C1-H) coupling constants determined from their proton-coupled C-13 NMR spectra. It was found that the values of the couplings are strongly dependent upon the type of substituent present, with powerful effects exerted by the halogens in particular. The IPPP-CLOPPA-INDO theoretical approach, which was employed to provide a measure of the extent of through-bond versus through-space transmission of coupling information, was found to give (3)J(C1-H) values in good agreement with experimental data. Empirical substituent parameter regressions were performed and found to be consistent with the CLOPPA description of the increase in both the through-bond and through-space contributions to the coupling. The substituent parameter regressional analyses also demonstrated that electronegativity effects play a predominant role in determining the magnitude of the couplings, particularly in those substrates in which the substituent is attached to the ring system by a second-row element.