2-(4'-fluoro-[1,1'-biphenyl]-2-yl)pyridine

• 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: 2-(4'-fluoro-[1,1'-biphenyl]-2-yl)pyridine
• 英文别名: 2-[2-(4-fluorophenyl)]phenylpyridine；2-[2-(4-Fluorophenyl)phenyl]pyridine
• 化学式: C₁₇H₁₂FN
• 分子量: 249.287
• InChiKey: HOLPTUYKCNKVMO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  12.9
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  rhodium(III) chloride trihydrate 、 2-(4'-fluoro-[1,1'-biphenyl]-2-yl)pyridine 以 乙二醇乙醚 、 水 为溶剂， 生成
  参考文献：
  名称：

  基于取代的2-苯基吡啶配体的环金属化铑（III）配合物：合成，结构，光物理，电化学和DNA结合特性

  摘要：

  一系列新的八面体的铑（III）络合物1 - 8的类型的[（L Ñ）2的Rh（dppz）] Cl（上Ñ = 1-6）和[（L Ñ）2的Rh（dppz）]（PF 6）{ n = 1、7、8; L = 2-苯基吡啶，具有不同的修饰，作为C，N-螯合配体；和dppz = dipyrido [3,2-a：2'，3'- c ]吩嗪}已被合成并充分表征。已经研究了配合物的光物理性质。五个配合物– [（L1）2 Rh（dppz）]（PF 6），[（L2）2 Rh（dppz）] Cl，[（L3）2Rh（dppz）]（PF 6），[（L4）2 Rh（dppz）]（PF 6）和[（L8）2 Rh（dppz）]（PF 6）–已经确认了预期的结构并揭示了取代对配合物结构的影响，这已经通过实验电化学表征得到了合理解释。配合物1 – 8的相互作用用小牛胸腺DNA（CT DNA）已通过荧光检测溴化乙锭（EB）的研究进行了

  DOI：

  10.1002/ejic.201700700
• 作为产物：
  描述：

  三正丁基2-吡啶基锌 在 bis(1,5-cyclooctadiene)nickel (0) 、 四(三苯基膦)钯 、 cesium fluoride 、 三环己基膦 作用下， 以 甲苯 为溶剂， 反应 12.0h， 生成 2-(4'-fluoro-[1,1'-biphenyl]-2-yl)pyridine
  参考文献：
  名称：

  Nickel-Catalyzed Suzuki–Miyaura Reaction of Aryl Fluorides

  摘要：

  Two protocols for the nickel-catalyzed cross-coupling of aryl fluorides with aryl boronic esters have been developed. The first employs metal fluoride cocatalysts, such as ZrF4 and TiF4, which enable Suzuki-Miyaura reactions of aryl fluorides bearing electron-withdrawing (ketones, esters, and CF3), aryl and alkenyl groups as well as those comprising fused aromatic rings, such as fluoronaphthalenes and fluoroquinolines. The second protocol employs aryl fluorides bearing ortho-directing groups, which facilitate the difficult C-F bond activation process via cyclometalation. N-heterocycles, such as pyridines, quinolines, pyrazoles, and oxazolines, can successfully promote cross-coupling with an array of organoboronic esters. A study into the substituent effects with respect to both coupling components has provided fundamental insights into the mechanism of the nickel-catalyzed cross-coupling of aryl fluorides.

  DOI：

  10.1021/ja207759e

文献信息

• Deliberately Losing Control of C−H Activation Processes in the Design of Small‐Molecule‐Fragment Arrays Targeting Peroxisomal Metabolism
  作者：Raysa Khan Tareque、Storm Hassell‐Hart、Tobias Krojer、Anthony Bradley、Srikannathasan Velupillai、Romain Talon、Michael Fairhead、Iain J. Day、Kamlesh Bala、Robert Felix、Paul D. Kemmitt、Paul Brennan、Frank Delft、Laura Díaz Sáez、Kilian Huber、John Spencer

  DOI：10.1002/cmdc.202000543

  日期：2020.12.15

  Combined photochemical arylation, “nuisance effect” (SNAr) reaction sequences have been employed in the design of small arrays for immediate deployment in medium‐throughput X‐ray protein–ligand structure determination. Reactions were deliberately allowed to run “out of control” in terms of selectivity; for example the ortho‐arylation of 2‐phenylpyridine gave five products resulting from mono‐ and bisarylations

  组合光化学芳基化、“滋扰效应”（ SN Ar）反应序列已被用于设计小型阵列，以便立即部署在中等通量 X 射线蛋白质-配体结构测定中。故意让反应在选择性方面“失控”；例如，2-苯基吡啶的邻位芳基化得到单芳基化和双芳基化与SNA Ar 工艺相结合的五种产物。结果，已经鉴定出许多针对 NUDT7（一种关键的过氧化物酶体 CoA 酯水解酶）的晶体学命中。
• Directed Palladium-Catalyzed Oxidative C-H Arylation of (Hetero)arenes with Arylboronic Acids by Using TEMPO
  作者：Armido Studer、Sylvia Kirchberg、Thomas Vogler

  DOI：10.1055/s-0028-1083546

  日期：——

  Oxidative coupling of three different arenes and a thiophene derivative with various arylboronic acids with Pd(OAc) 2 and the commercially available 2,2,6,6-tetramethylpiperidine-N-oxyl radical (TEMPO) as an oxidant are reported. A 2-pyridyl group on the substrates serves as ortho-directing group to mediate the C-H arylation. Mechanistic studies are provided.

  报道了三种不同的芳烃和噻吩衍生物与各种芳基硼酸与 Pd(OAc) 2 和作为氧化剂的市售 2,2,6,6-四甲基哌啶-N-氧基自由基 (TEMPO) 的氧化偶联。底物上的 2-吡啶基用作邻位导向基团以介导 CH 芳基化。提供了机理研究。
• Palladium(II)-Catalyzed ortho Arylation of 2-Phenylpyridines with Potassium Aryltrifluoroborates by C-H Functionalization
  作者：Ming-Jung Wu、Jean-Ho Chu、Shiang-Lin Tsai

  DOI：10.1055/s-0029-1217014

  日期：2009.11

  4-dioxane at 120 ˚C for 24 hours. p-Benzoquinone is an important co-oxidant in the transmetalation-reductive elimination step. The kinetic isotope effect (k H/k D) for the C-H bond activation was determined to be 1.09. It indicates that the C-H bond cleavage does not occur in the rate-determining step. C-H functionalization - potassium trifluoroborate - palladium catalyst - arylations - pyridines

  提出了通过使用芳基三氟硼酸钾有效地一锅合成邻芳基化的2-苯基吡啶和吡啶衍生物。最佳反应条件如下：在10摩尔％的乙酸钯（II），三当量的乙酸铜（II）和两当量的乙酸铜存在下，用2.5当量的芳基三氟硼酸钾处理2-苯基吡啶或吡啶衍生物。对苯醌在1,4-二恶烷中的溶液在120°C下保持24小时。对苯醌是在金属转移-还原消除步骤中的重要助氧化剂。动力学同位素效应（k H / k D对于CH键的活化确定为1.09。这表明在速率确定步骤中没有发生CH键断裂。 CH官能化-三氟硼酸钾-钯催化剂-芳基化-吡啶
• Nickel‐Catalyzed Intramolecular Coupling of Sulfones via the Extrusion of Sulfur Dioxide
  作者：Tian‐Yang Yu、Zhao‐Jing Zheng、Jing‐Hua Bai、Hong Fang、Hao Wei

  DOI：10.1002/adsc.201801733

  日期：2019.4.23

  We describe a method for intramolecular desulfonylative coupling using bis(cyclooctadiene)nickel as a catalyst. A broad range of aromatic, heteroaromatic and aliphatic sulfones can be utilized as substrates in this process. This method provides an atom‐economical route to the synthesis of various biaryls and an efficient tool for the catalytic conversion of sulfonyl groups, representing a significant

  我们描述了一种使用双（环辛二烯）镍作为催化剂的分子内脱磺酰基偶联的方法。在该方法中，可以使用各种各样的芳族，杂芳族和脂族砜作为底物。该方法为各种联芳基的合成提供了一种原子经济的途径，也是磺酰基催化转化的有效工具，代表了有机合成的重大进展
• Palladium-Catalyzed Decarboxylative Arylation of C−H Bonds by Aryl Acylperoxides
  作者：Wing-Yiu Yu、Wing Nga Sit、Zhongyuan Zhou、Albert S.-C. Chan

  DOI：10.1021/ol900756g

  日期：2009.8.6

  bond was developed using aryl acylperoxides as inexpensive aryl sources. Substrates containing pyridyl, oxime, and oxazoline groups undergo effectively ortho-selective C−H arylation with excellent functional group tolerance. This arylation should begin by directing-group-assisted cyclopalladation, followed by the reaction of the palladacycle with aryl radicals generated in situ by thermal decomposition

  使用芳基酰基过氧化物作为廉价的芳基来源，开发了Pd（OAc）2催化的芳族CH键的脱羧芳基化反应方案。含有吡啶基，肟和恶唑啉基团的底物可进行有效的邻位选择性CH芳基化反应，并具有出色的官能团耐受性。这种芳基化反应应首先通过引导基团辅助的环钯反应，然后使Palladacycle与过氧化物热分解就地生成的芳基发生反应。