- HETEROCYCLIC COMPOUND AND ORGANIC LIGHT-EMITTING DEVICE INCLUDING THE SAME
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Provided are a heterocyclic compound represented by Formula 1 and an organic light-emitting device including the same. The organic light-emitting device includes: a first electrode; a second electrode facing the first electrode; and an organic layer betwe
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Paragraph 0479-0481
(2021/11/20)
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- One-Pot C-H Arylation/Lactamization Cascade Reaction of Free Benzylamines
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An efficient method has been developed for the synthesis of seven-membered biaryl lactams involving Pd-catalyzed, native amine-directed, ortho-arylation of benzylamines followed by in situ lactamization. This cascade sequence is enabled by the use of 2-iodobenzoates, which facilitates C-H arylation from the free amine under conditions that typically require an improved directing group approach. This reaction is characterized by a broad substrate scope with good functional group tolerance. The need for an ester versus carboxylic acid-functionalized coupling partner is also explored, as is the potential for synthesizing eight-membered biaryl lactams. Various applications are also investigated, including access to the aza-brassinolide core.
- Chand-Thakuri, Pratibha,Landge, Vinod G.,Kapoor, Mohit,Young, Michael C.
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supporting information
p. 6626 - 6644
(2020/07/14)
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- Synthesis of 4H-1,3-Benzoxazines via Metal- and Oxidizing Reagent-Free Aromatic C-H Oxygenation
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An unprecedented electrochemical aromatic C-H oxygenation reaction for the synthesis of 4H-1,3-benzoxazines from easily available N-benzylamides is reported. These oxidative cyclization reactions proceed in a transition metal- and oxidizing reagent-free fashion and produce H2 as only theoretical byproduct. Adapting the C-H oxygenation reaction in an electrochemical microreactor has been demonstrated.
- Xu, Fan,Qian, Xiang-Yang,Li, Yan-Jie,Xu, Hai-Chao
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supporting information
p. 6332 - 6335
(2017/12/08)
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- A Rapid Injection NMR Study of the Reaction of Organolithium Reagents with Esters, Amides, and Ketones
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Unexpectedly high rates of reaction between alkyllithium reagents and amides, compared to esters and ketones, were observed by Rapid Inject NMR and competition experiments. Spectroscopic investigations with 4-fluorophenyllithium (ArLi, mixture of monomer and dimer in THF) and a benzoate ester identified two reactive intermediates, a homodimer of the tetrahedral intermediate, stable below -100°C, and a mixed dimer with ArLi. Direct formation of dimers suggested that the ArLi dimer may be the reactive aggregate rather than the usually more reactive monomer. In contrast, RINMR experiments with ketones demonstrated that the ArLi monomer was the reactive species. (Chemical Equation Presented).
- Plessel, Kristin N.,Jones, Amanda C.,Wherritt, Daniel J.,Maksymowicz, Rebecca M.,Poweleit, Eric T.,Reich, Hans J.
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supporting information
p. 2310 - 2313
(2015/05/27)
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- Carbocation-forming reactions in ionic liquids
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A number of trifluoroacetates, mesylates, and triflates have been studied in ionic liquids. Several lines of evidence indicate that all of these substrates react via ionization to give carbocationic intermediates. For example, cumyl trifluoroacetates give mainly the elimination products, but the Hammett ρ+ value of -3.74 is consistent with a carbocationic process. The analogous exo-2-phenyl-endo-3-deutero-endo-bicyclo-[2.2.1]hept-2-yl trifluoroacetate gives an elimination where loss of the exo-hydrogen occurs from a cationic intermediate. 1-Adamantyl mesylate and 2-adamantyl triflate react to give simple substitution products derived from capture of 1- and 2-adamantyl carbocations by the residual water in the ionic liquid. The triflate derivative of pivaloin, trans-2-phenylcyclopropylcarbinyl mesylate, 2,2-dimethoxycyclobutyl triflate, the mesylate derivative of diethyl (phenylhydroxymethyl)-thiophosphonate, and Z-1-phenyl-5-trimethylsilyl-3-penten- 1-yl trifluoroacetate all give products derived carbocation rearrangements (kΔ processes), anti-7-Norbornenyl mesylate gives products with complete retention of configuration, indicative of involvement of the delocalized 7-norbornenyl cation. 1,6-Methano[10]annulen-11-yl triflate reacts in [BMIM][NTf2] to give 1,6-methano[10]annulen-11-ol, along with naphthalene, an oxidized product derived from loss of trifluoromethanesulfinate ion. Analogous loss of CF3SO2- can be seen in reaction of PhCH(CF3)OTf. Ionic liquids are therefore viable solvents for formation of carbocationic intermediates via kc and k Δ processes.
- Creary, Xavier,Willis, Elizabeth D.,Gagnon, Madeleine
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p. 18114 - 18120
(2007/10/03)
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- A comparison of substituent effects on the stability of α,α-dimethylbenzyl carbocations in aqueous solution and in the gas phase: How significant is nucleophilic solvation?
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Rate and equilibrium constants for conversion of ring-substituted cumyl alcohols in acidic solutions of 50:50 (v/v) trifluoroethanol/water (I = 0.50, NaClO4) to an equilibrium mixture of the corresponding cumyl alcohol, cumyl trifluoroethyl ether, and α-methylstyrene and the fractional yields of cumyl trifluoroethyl ether obtained from partitioning of the cumyl carbocation intermediates of these reactions between capture by water and by trifluoroethanol have been determined. These data and estimates of absolute rate constants for the reaction of ring-substituted cumyl carbocations with water in 50:50 (v/v) trifluoroethanol/water30 have been used to calculate equilibrium constants KR and Kp respectively for conversion of ring-substituted cumyl carbocations to the corresponding cumyl alcohols and α-methylstyrenes and the changes in Gibbs free energy (△Gx)sol for deprotonation of ring-substituted cumyl carbocations by α-methylstyrene. A plot of (△Gx)sol against (△Gx)gas for the corresponding reactions in the gas phase is linear with a slope of 0.70, in contrast to the previously reported unitary slopes of correlations of substituent effects on carbocation stability in solution and in the gas phase. We conclude that there is a modest increase in the stabilization of ring-substituted cumyl carbocations by solvation as their stability is decreased, but that this is much smaller than the change in stabilization by solvation with the changing stability of pyridinium and anilinium ions. The possible relevance of these data to the stabilization of carbocations by nucleophilic solvation is discussed.
- Richard, John P.,Jagannadham, Vandannapu,Amyes, Tina L.,Mishima, Masaaki,Tsuno, Yuho
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p. 6706 - 6712
(2007/10/02)
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