78881-21-7Relevant articles and documents
Synthesis of new cyano-substituted analogues of Tr?ger's bases from bromo-derivatives. A stereochemical dependence of long-range (nJHH, n?=?4, 5, and 6) proton–proton and proton–carbon (nJCH, n?=?1, 2, 3, 4, and 5) coupling constants of these compounds
Dusso, Diego,Ramirez, Cristina,Parise, Alejandro,Lanza,Vera, D. Mariano,Chesta, Carlos,Moyano, E. Laura,Akhmedov, Novruz G.
, p. 423 - 454 (2019/05/24)
A free-catalyst microwave-assisted cyanation of brominated Tr?ger's base derivatives (2a-f) is reported. The procedure is simple, efficient, and clean affording the nitrile compounds (3a-e, I) in very good yields. Complete assignment of 1H and 13C chemical shifts of 2a-f, I and 3a-d, I was achieved using gradient selected 1D nuclear magnetic resonance (NMR) techniques (1D zTOCSY, PSYCHE, DPFGSE NOE, and DEPT), homonuclear 2D NMR techniques (gCOSY and zTOCSY), and heteronuclear 2D NMR techniques (gHSQCAD/or pure-shift gHSQCAD, gHMBCAD, bsHSQCNOESY, and gHSQCAD-TOCSY) with adiabatic pulses. Determination of the long-range proton–proton coupling constants nJHH (n?=?4, 5, 6) was accomplished by simultaneous irradiation of two protons at appropriate power levels. In turn, determined coupling constants were tested by an iterative simulation program by calculating the 1H NMR spectrum and comparing it to the experimental spectrum. The excitation-sculptured indirect-detection experiment (EXSIDE) and 1H-15N CIGARAD-HMBC (constant time inverse-detection gradient accordion rescaled heteronuclear multiple bond correlation) were applied for determination of long-range carbon–proton coupling constants nJCH (n?=?2, 3, and 4) and for assignment of 15N chemical shift at natural abundance, respectively. DFT/B3LYP optimization studies were performed in order to determine the geometry of 2c using 6-31G(d,p), 6-311G(d,p), and 6–311?+?G(d,p) basis sets. For calculation of 1H and 13C chemical shifts, nJHH (n?=?2, 3, 4, 5, and 6), and nJCH (n?=?1, 2, 3, and 4) coupling constants, the GIAO method was employed at the B3LYP/6-31G(d,p), B3LYP/6-31+G(d,p), B3LYP/6-311+G(d,p), B3LYP/6-311++G(2d,2p), B3LYP/cc-pVTZ), and B3LYP/aug-cc-pVTZ) levels of theory. For the first time, a stereochemical dependence magnitude of the long-range nJHH (n?=?4, 5, and 6) and nJCH (n?=?1, 2, 3, 4, and 5) have been found in bromo-substituted analogues of Tr?ger's bases.
Pd-Catalyzed Cyanation of (Hetero)Aryl Halides by Using Biphosphine Ligands
Zhang, Shaoke,Neumann, Helfried,Beller, Matthias
supporting information, p. 67 - 70 (2017/11/27)
Tetraadamantylbiphosphine (TABP; L1), which showed superior activity in the palladium-catalyzed cyanation of 4-chloroanisole compared to standard phosphines, was synthesized as a new ligand. The generality of the new catalytic system was shown by the cyanation reaction of approximately 30 (hetero)aryl halides including hindered, electron-rich, and electron-poor aryl chlorides. These reactions constitute the first examples of using biphosphine ligands in Pd-catalyzed coupling reactions.
Synthesis, insecticidal activities and SAR of novel phthalamides targeting calcium channel
Chen, Youwei,Li, Yuxin,Pan, Li,Liu, Jingbo,Wan, Yingying,Chen, Wei,Xiong, Lixia,Yang, Na,Song, Haibin,Li, Zhengming
, p. 6366 - 6379 (2015/01/09)
In order to find novel and environmental friendly insecticides targeting the ryanodine receptor, three series of novel phthalamides containing heptafluoroisopropyl group, low fluorine atoms group and non-fluorine group were designed and synthesized. 35 novel structures of three series were obtained. Insecticidal activities of title compounds against oriental armyworm (Mythimna separata) and diamondback moth (Plutella xylostella) indicated that most of title compounds showed moderate to high activities at the tested concentration. The structure-activity relationship (SAR) was discussed in detail. During synthesizing title compounds B8, C7, D1, D9 and D12, their corresponding positional isomers (B8′, C7′, D1′, D9′ and D12′) were afforded, and their structures were confirmed by 2D NMR. The calcium-imaging technique was also applied to investigate the effects of compounds B2, B10, C4 and C5 on the intracellular calcium ion concentration ([Ca2+]i), which indicated that they released stored calcium ions from endoplasmic reticulum, which denoted that some compounds are potential modulators of the insect ryanodine receptor (RyR).
