2113-51-1Relevant articles and documents
Synthesis and stereochemical studies of di and tetra 9,9′- spirobifluorene porphyrins: New building blocks for catalytic material
Poriel, Cyril,Ferrand, Yann,Juillard, Sandrine,Le Maux, Paul,Simonneaux, Gérard
, p. 145 - 158 (2004)
We report the synthesis and stereochemical properties of a new class of molecules containing a covalently-linked porphyrin and spiro-9,9′- bifluorene derivatives. The large spiro substituents hinder rotation about the meso position to give atropisomers which can be detected by 1H NMR after phosphine or isocyanide complexation to the ruthenium spiroporphyrins.
Pt(II) metal complexes tailored with a newly designed spiro-arranged tetradentate ligand; Harnessing of charge-transfer phosphorescence and fabrication of sky blue and white OLEDs
Liao, Kuan-Yu,Hsu, Che-Wei,Chi, Yun,Hsu, Ming-Kuan,Wu, Szu-Wei,Chang, Chih-Hao,Liu, Shih-Hung,Lee, Gene-Hsiang,Chou, Pi-Tai,Hu, Yue,Robertson, Neil
, p. 4029 - 4038 (2015)
Tetradentate bis(pyridyl azolate) chelates are assembled by connecting two bidentate 3-trifluoromethyl-5-(2-pyridyl)azoles at the six position of pyridyl fragment with the tailored spiro-arranged fluorene and/or acridine functionalities. These new chelates were then utilized in synthesizing a series of Pt(II) metal complexes [Pt(Ln)], n = 1-5, from respective chelates L1-L5 and [PtCl2(DMSO)2] in 1,2-dimethoxyethane. The single-crystal X-ray structural analyses were executed on 1, 3, and 5 to reveal the generalized structures and packing arrangement in crystal lattices. Their photophysical properties were measured in both solution and solid state and are discussed in the context of computational analysis. These L1-L5 coordinated Pt(II) species exhibit intense emission, among which complex 5 shows remarkable solvatochromic phosphorescence due to the dominant intraligand charge transfer transition induced by the new bis(pyridyl azolate) chelates. Moreover, because of the higher-lying highest occupied molecular orbital of acridine, complex 5 can be considered as a novel bipolar phosphor. Successful fabrication of blue and white organic light-emitting diodes (OLEDs) using Pt(II) complexes 3 and 5 as the phosphorescent dopants are reported. In particular, blue OLEDs with 5 demonstrated peak efficiencies of 15.3% (36.3 cd/A, 38.0 lm/W), and CIE values of (0.190, 0.342) in a double-emitting layer structure. Furthermore, a red-emitting Os(II) complex and 5 were used to fabricate warm-white OLEDs to achieve peak external quantum efficiency, luminance efficiency, and power efficiency values as high as 12.7%, 22.5 cd/A, and 22.1 lm/W, respectively.
Synthesis of 4-alkylidene-substituted 1,2,3,4-tetrahydroisoquinolines via palladium-catalyzed carbopalladation/C-H activation of 2-bromobenzyl-N-propargylamines
Naveen, Kanagaraj,Nandakumar, Avanashiappan,Perumal, Paramasivan Thirumalai
, p. 1633 - 1642 (2015)
Abstract Tetrasubstituted alkene-based 1,2,3,4-tetrahydroisoquinolines are synthesized via the formation of a cyclic carbopalladation complex followed by C-H bond activation of the sp2 carbon in arenes. This domino reaction proceeds with good selectivity and provides good yields of the products. The requisite starting materials are synthesized by copper(I) iodide catalyzed A3-coupling reactions.
Pd-Catalyzed C(sp3)-H Biarylation via Transient Directing Group Strategy
Ding, Mingruo,Hua, Wenkai,Liu, Min,Zhang, Fengzhi
, p. 7419 - 7423 (2020)
Here, we describe a highly selective Pd-catalyzed C(sp3)-H biarylation of 2-methylbenzaldehydes using cyclic diaryliodonium salts as arylation reagents. The key strategy is the employment of tert-leucine as a bidentate transient directing group for the proximity-driven metalation to achieve reactivity and selectivity in C-H activation. Various functionalized biaryls bearing both aldehyde and iodine functional groups were prepared successfully, which could be further transformed into a wide range of compounds with potential applications in pharmaceutical chemistry and materials science.
N-Heterocyclic Iod(az)olium Salts – Potent Halogen-Bond Donors in Organocatalysis
Boelke, Andreas,Kuczmera, Thomas J.,Lork, Enno,Nachtsheim, Boris J.
supporting information, p. 13128 - 13134 (2021/08/09)
This article describes the application of N-heterocyclic iod(az)olium salts (NHISs) as highly reactive organocatalysts. A variety of mono- and dicationic NHISs are described and utilized as potent XB-donors in halogen-bond catalysis. They were benchmarked in seven diverse test reactions in which the activation of carbon- and metal-chloride bonds as well as carbonyl and nitro groups was achieved. N-methylated dicationic NHISs rendered the highest reactivity in all investigated catalytic applications with reactivities even higher than all previously described monodentate XB-donors based on iodine(I) and (III) and the strong Lewis acid BF3.
Iodine-Catalyzed Methylthiolative Annulation of 2-Alkynyl Biaryls with DMSO: A Metal-Free Approach to 9-Sulfenylphenanthrenes
Chatterjee, Tanmay,Mukherjee, Nilanjana
, p. 7881 - 7890 (2021/06/28)
An iodine-catalyzed sustainable, cost-effective, and atom-economic synthetic methodology is developed to synthesize a wide variety of valuable sulfenylphenanthrenes and polycyclic heteroaromatics in moderate to high yield through electrophilic thiolative annulation of 2-alkynyl biaryls (6-endo-dig cyclization) using methyl sulfoxides such as dimethyl sulfoxide (DMSO) as the sulfur source under transition-metal-free conditions. The transformation requires only iodine in a catalytic amount and trifluoroacetic anhydride. Notably, DMSO played multiple roles such as methylthiolating reagent, oxidant, and solvent in this reaction.
Modular Tandem Mizoroki-Heck/Reductive Heck Reactions to Construct Fluorenes from Cyclic Diaryliodoniums
Peng, Xiaopeng,Yang, Yang,Luo, Bingling,Wen, Shijun,Huang, Peng
supporting information, p. 222 - 226 (2020/12/01)
Starting from cyclic diaryliodoniums and terminal alkenes, a diverse set of fluorenes is conveniently constructed. The reactions catalyzed by palladium undergo one conventional Mizoroki-Heck reaction and one reductive Heck reaction. The scope of alkenes is general, leading to 29 fluorenes which would expand the structural diversity of fluorene reservoir. (Figure presented.).
Palladium-Catalyzed [4 + 3] or [2 + 2 + 3] Annulation via C-H Activation and Subsequent Decarboxylation: Access to Heptagon-Embedded Polycyclic Aromatic Hydrocarbons
Yang, Xiumei,Chen, Xiahong,Xu, Yankun,Zhang, Minghao,Deng, Guobo,Yang, Yuan,Liang, Yun
supporting information, p. 2610 - 2615 (2021/04/12)
The construction of a seven-membered ring in the polycyclic aromatic hydrocarbon skeleton remains a notoriously difficult but attractive challenge. Herein a novel palladium-catalyzed [4 + 3] decarboxylative annulation of 2-iodobiphenyls with 2-(2-halophenyl)acrylic acids is reported, which provides an efficient approach for assembling various tribenzo[7]annulenes via a C-H activation and decarboxylation process. Moreover, tribenzo[7]annulenes can be also synthesized via a [2 + 2 + 3] decarboxylative annulation strategy by employing readily available 1,2-halobenzenes, phenylboronic acids, and 2-(2-halophenyl)acrylic acids.
Atmosphere-Controlled Palladium-Catalyzed Divergent Decarboxylative Cyclization of 2-Iodobiphenyls and α-Oxocarboxylic Acids
Zhou, Liwei,Sun, Mingjie,Zhou, Fengru,Deng, Guobo,Yang, Yuan,Liang, Yun
supporting information, p. 7150 - 7155 (2021/09/18)
A novel palladium-catalyzed divergent decarboxylative cyclization of 2-iodobiphenyls and α-oxocarboxylic acids utilizing the atmosphere as a controlled switch is reported. Under the protection of a nitrogen atmosphere, tribenzotropones are synthesized by a [4 + 3] decarboxylative cyclization. Employing a palladium/O2 system enables a [4 + 2] decarboxylative cyclization to assemble triphenylenes. Notably, preliminary mechanistic studies indicate that the formation of triphenylenes involves a double decarboxylation.
Scalable electrochemical synthesis of diaryliodonium salts
Elsherbini, Mohamed,Moran, Wesley J.
supporting information, p. 4706 - 4711 (2021/06/11)
Cyclic and acyclic diaryliodonium are synthesised by anodic oxidation of iodobiaryls and iodoarene/arene mixtures, respectively, in a simple undivided electrolysis cell in MeCN-HFIP-TfOH without any added electrolyte salts. This atom efficient process does not require chemical oxidants and generates no chemical waste. More than 30 cyclic and acyclic diaryliodonium salts with different substitution patterns were prepared in very good to excellent yields. The reaction was scaled-up to 10 mmol scale giving more than four grams of dibenzo[b,d]iodol-5-ium trifluoromethanesulfonate (>95%) in less than three hours. The solvent mixture of the large-scale experiment was recovered (>97%) and recycled several times without significant reduction in yield.
