6-(tert-butyl)-2,2'-bipyridine | 150205-22-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: 6-(tert-butyl)-2,2'-bipyridine
• 英文别名: 6-t-Butyl-2,2'-bipyridine；2-tert-butyl-6-pyridin-2-ylpyridine
• CAS: 150205-22-4
• 化学式: C₁₄H₁₆N₂
• 分子量: 212.294
• InChiKey: NZNVZDDBBNWKOQ-UHFFFAOYSA-N

物化性质

• 沸点：
  320.6±30.0 °C(Predicted)
• 密度：
  1.021±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  25.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  6-(tert-butyl)-2,2'-bipyridine 在 HCl 作用下， 以 水 、 丙酮 为溶剂， 生成
  参考文献：
  名称：

  Cyclopalladation of 6-Substituted-2,2‘-bipyridines. Metalation of Unactivated Methyl Groups vs Aromatic C−H Activation

  摘要：

  6-Alkyl-2,2'-bipyridines, HL, (N2C10H7R; R = CH2Me, HLet; CHMe2, HLip; CMe3, HLtb, CH2CMe3, HLnp, CMe2Ph, HLdm) react with Na-2[PdCl4] to give either 1:1 adducts [Pd(HL)Cl-2] (HLet, HLip, HLnp) or cyclometalated complexes [Pd(L)Cl] (HLtb, HLdm). Reaction of palladium(II) acetate, followed by exchange with LiCl, affords a series of cyclopalladated species [Pd(L)Cl] where L is a terdentate anionic N-N-C ligand which originates from HL through direct activation of a C(sp(3))-H or a C(sp(2))-H bond. The structures of [Pd(L-tb)Cl] and [Pd(L-np)Cl], which contain a [5,5] ora [5,6] fused ring system, respectively, have been determined by X-ray diffraction and are compared. In the case of the ligand HLip, three different cyclometalated species have been isolated, [Pd(L)Cl], [Pd(L)Cl](2), and [Pd{N2C10H7[CH(CH2-OC(O)CH3)(CH2)}Cl] the latter one arising from activation of both methyl groups of the substituent. The isolation of two [Pd(L-dm)Cl] species (compounds 8 and 9), having an aromatic or an aliphatic carbon-metal bond, respectively, is an example of isomerism, still rare in organometallic chemistry.

  DOI：

  10.1021/om000239o
• 作为产物：
  描述：

  6-bromo-6′-(tert-butyl)-2,2′-bipyridine 在 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 反应 0.22h， 以65%的产率得到6-(tert-butyl)-2,2'-bipyridine
  参考文献：
  名称：

  通过铜-联吡啶催化的α-氨基苄基硼酸酯的分子内偶联，在硼结合的立体中心形成立体反转CC键。

  摘要：

  通过使用具有2,2'-联吡啶的非手性配体的铜催化剂，可以实现与α-（2-卤代苯甲酰基氨基）苄基硼酸酯的对映体分子内Suzuki-Miyaura型偶联，生成3-取代的异吲哚啉酮。在具有高对映体特异性的6-苯基-2,2'-联吡啶配体的存在下，在硼结合的立体碳上带有氢原子的对映体富集的α-氨基苄基硼反应物进行立体反转偶联。在存在简单的2,2'-联吡啶作为配体的情况下，带有完全取代的与硼结合的立体成核中心的α-氨基苄基硼酸酯也给出了3,3-二取代的异吲哚啉酮，具有立体定向的立体化学转化作用。

  DOI：

  10.1002/anie.201914864

文献信息

• N,C “Rollover” Cyclometalated Platinum(II) Hydrides: Mono- and Polynuclear Derivatives
  作者：Giovanni Minghetti、Sergio Stoccoro、Maria Agostina Cinellu、Giacomo Luigi Petretto、Antonio Zucca

  DOI：10.1021/om800027g

  日期：2008.7.1

  cyclometalated platinum(II) hydrides were obtained by reaction of the “rollover” derivatives [Pt(N′−C(3))(Cl)(L)] (N−CH= 6-tert-butyl- and 6-phenyl-2,2′-bipyridine; L = DMSO, 3,5-Me2-pyridine, PPh3) with Na[BH4]. Mono- or polynuclear hydrides, [Pt(N′−C(3))(H)(L)] or [Pt(N′−C(3))(μ-H)]n, are formed depending on the nature of the neutral ligand, L. The unsaturated 14-electron fragments [Pt(N′−C(3))(μ-H)] assemble

  通过“侧翻”衍生物[PT（N'-C（3））（Cl）（L）]（N-CH = 6-叔丁基-和6 -苯基-2,2'-联吡啶； L = DMSO，3,5-Me 2-吡啶，PPh 3），具有Na [BH 4 ]。单核或多核的氢化物，[PT（N'-C（3））（H）（L）]或[PT（N'-C（3））（μ-H）] Ñ，形成取决于性质不饱和的14电子片段[PT（N'-C（3））（μ-H）]组装形成带有桥联氢化物的低聚物。光谱表征为溶液（1 H NMR）和气相（ESI-MS）中的四聚体提供了证据。在四聚体系统中，2e-3c PT-H-PT键被π-受体配体（例如Ph 3）裂解P和CO生成稳定的单核氢化物。
• Chiral spiro Cu(i) complexes. Supramolecular stereocontrol and isomerisation dynamics by the use of TRISPHAT anions
  作者：Virginie Hebbe-Viton、Val?rie Desvergnes、Jonathan J. Jodry、Christiane Dietrich-Buchecker、Jean-Pierre Sauvage、J?r?me Lacour

  DOI：10.1039/b515540a

  日期：——

  Association of enantiopure TRISPHAT anion (1) with chiral spiro [Cu(LL′)2] complexes (LL′ = 2-R-phen, 2, 6-R-bpy, 3, and 2-iminopyridine, 4) leads to an efficient NMR enantiodifferentiation. Variable temperature 1H NMR spectroscopy has been used to determine the isomerisation kinetics of these pseudo-tetrahedral complexes and to evaluate their configurational stability; the latter depending on the structure of the diimine ligands. In the case of the 2-anthracenyl-phen derivative, a decent level of supramolecular stereocontrol was noted (d.e. up to 45%); the configuration of the complex being determined by electronic circular dichroism (ECD).

  与手性螺旋[Cu(LL′)2]复合物（LL′ = 2-R-苯，2,6-R-bpy，3和2-亚氨基吡啶，4）结合的手性纯TRISPHAT阴离子（1）导致了高效的NMR手性分离。采用可变温度1H NMR光谱法确定了这些伪四面体复合物的异构化动力学，并评估了其构型稳定性；后者取决于二亚胺配体的结构。在2-蒽基-苯衍生物的情况下，观察到相当程度的超分子立体控制（立体选择性高达45%）；该复合物的构型通过电子圆二色性（ECD）确定。
• Cyclometallated derivatives of platinum(<scp>II</scp>) derived from 6-(tert-butyl)-2,2′-bipyridine (HL). Crystal and molecular structure of [Pt(L)CI]
  作者：Giovanni Minghetti、Maria Agostina Cinellu、Sergio Stoccoro、Antonio Zucca、Mario Manassero

  DOI：10.1039/dt9950000777

  日期：——

  in good yields. With potentially bidentate neutral ligands, L″–L″[Ph2P(CH2)2PPh2(dppe), Ph2P(CH2)2AsPh2(dadpe) or Ph2PCCPPh2(dppa)], [LPt(µ–L″–L″)PtL]2+(L″–L″= dppe 5, dadpe 6 or dppa 7) or [PtL(L″–L″)]+ species (L″–L″= dppe 8 or dadpe 9) can be obtained by adequate choice of the L″–L″ : Pt molar ratio (1 : 2 or 1 : 1, respectively). The new complexes 1–9 were characterized in solution by 1H, 13C-1H}

  K 2 [PtCI 4 ]与6-（叔丁基）-2,2'-联吡啶（HL）的反应使[Pt（L）CI] 1a环化金属，这是由于甲基CH键的直接活化而产生的。结构已经通过X射线衍射确定。晶体包含两个独立的分子：主要参数的平均值为Pt–CI 2.300，Pt–C 2.003，Pt–N（反式至C）2.114和Pt–N（反式CI）1.948Å。1a中的氯原子很容易被中性配体（L'）取代；在NaBF 4存在下，阳离子种类[Pt（L）（L'）] [BF 4 ]（L'= PPh 3 2，CO 3或3，5-二甲基吡啶4）以高收率分离。具有潜在的双齿中性配体L“ –L” [Ph 2 P（CH 2）2 PPh 2（dppe），Ph 2 P（CH 2）2 AsPh 2（dappe）或Ph 2 PC CPPh 2（dppa）]， [LPt（µ–L“ –L”）PtL] 2+（L“ –L” = dppe 5，dadpe 6或dppa
• The shiny side of copper: bringing copper(<scp>i</scp>) light-emitting electrochemical cells closer to application
  作者：Sarah Keller、Alessandro Prescimone、Maria-Grazia La Placa、José M. Junquera-Hernández、Henk J. Bolink、Edwin C. Constable、Michele Sessolo、Enrique Ortí、Catherine E. Housecroft

  DOI：10.1039/d0ra03824e

  日期：——

  Heteroleptic [Cu(P^P)(N^N)][PF6] complexes, where N^N is 5,5′-dimethyl-2,2′-bipyridine (5,5′-Me2bpy), 4,5,6-trimethyl-2,2′-bipyridine (4,5,6-Me3bpy), 6-(tert-butyl)-2,2′-bipyridine (6-tBubpy) and 2-ethyl-1,10-phenanthroline (2-Etphen) and P^P is either bis(2-(diphenylphosphino)phenyl)ether (POP, PIN [oxydi(2,1-phenylene)]bis(diphenylphosphane)) or 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (xantphos

  杂配 [Cu(P^P)(N^N)][PF 6 ] 配合物，其中 N^N 是 5,5'-二甲基-2,2'-联吡啶 (5,5'-Me 2 bpy), 4 ,5,6-trimethyl-2,2'-bipyridine (4,5,6-Me 3 bpy), 6-( tert -butyl)-2,2'-bipyridine (6- t Bubpy) 和 2-ethyl- 1,10-菲咯啉 (2-Ethphen) 和 P^P 是双(2-(二苯基膦基)苯基)醚 (POP, PIN [oxydi(2,1-phenylene)]bis(diphenylphosphane)) 或 4,5-合成了双(二苯基膦)-9,9-二甲基氧杂蒽(xantphos, PIN (9,9-dimethyl-9 H -xanthene-4,5-diyl)bis(diphenylphosphane))，并对其进行核磁共振光谱、质谱、结
• Aryl‐to‐Vinyl 1,4‐Nickel Migration/Reductive Cross‐Coupling Reaction for the Stereoselective Synthesis of Multisubstituted Olefins
  作者：Cui‐Tian Wang、Peng‐Yu Liang、Ming Li、Bin Wang、Yu‐Zhao Wang、Xue‐Song Li、Wan‐Xu Wei、Xue‐Ya Gou、Ya‐Nan Ding、Zhe Zhang、Yu‐Ke Li、Xue‐Yuan Liu、Yong‐Min Liang

  DOI：10.1002/anie.202304447

  日期：2023.7.10

  The 1,4-nickel migration process from aryl to alkenyl groups is now reported for the first time. The alkenyl nickel intermediates generated by this highly stereoselective migration process can be coupled with brominated alkanes to form multisubstituted olefins. The current method provides a new and efficient approach for the synthesis of Z/E olefins with high stereoselectivity.

  首次报道了 1,4-镍从芳基到烯基的迁移过程。这种高度立体选择性迁移过程产生的烯基镍中间体可以与溴化烷烃偶联形成多取代烯烃。该方法为高立体选择性Z / E烯烃的合成提供了一种新的、高效的方法。