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151.
Mahdiar Khakinejad Samaneh Ghassabi Kondalaji Gregory C. Donohoe Stephen J. Valentine 《Journal of the American Society for Mass Spectrometry》2016,27(3):462-473
Gas-phase hydrogen deuterium exchange (HDX), collision cross section (CCS) measurement, and molecular dynamics simulation (MDS) techniques were utilized to develop and compare three methods for estimating the relative surface area exposure of separate peptide chains within bovine insulin ions. Electrosprayed [M – 3H]3? and [M – 5H]5? insulin ions produced a single conformer type with respective collision cross sections of 528 ± 5 Å2 and 808 ± 2 Å2. [M – 4H]4? ions were comprised of more compact (Ω = 676 ± 3 Å2) and diffuse (i.e., more elongated, Ω = 779 ± 3 Å2) ion conformer types. Ions were subjected to HDX in the drift tube using D2O as the reagent gas. Collision-induced dissociation was used to fragment mobility-selected, isotopically labeled [M – 4H]4? and [M – 5H]5? ions into the protein subchains. Deuterium uptake levels of each chain can be explained by limited inter-chain isotopic scrambling upon collisional activation. Using nominal ion structures from MDS and a hydrogen accessibility model, the deuterium uptake for each chain was correlated to its exposed surface area. In separate experiments, the per-residue deuterium content for the protonated and deprotonated ions of the synthetic peptide KKDDDDDIIKIIK were compared. The differences in deuterium content indicated the regional HDX accessibility for cations versus anions. Using ions of similar conformational type, this comparison highlights the complementary nature of HDX data obtained from positive- and negative-ion analysis. 相似文献
152.
Payam Abdolalian Samaneh K. Tizhoush Kaveh Farshadfar Alireza Ariafard 《Chemical science》2021,12(20):7185
Although Pd(OAc)2-catalysed alkoxylation of the C(sp3)–H bonds mediated by hypervalent iodine(iii) reagents (ArIX2) has been developed by several prominent researchers, there is no clear mechanism yet for such crucial transformations. In this study, we shed light on this important issue with the aid of the density functional theory (DFT) calculations for alkoxylation of butyramide derivatives. We found that the previously proposed mechanism in the literature is not consistent with the experimental observations and thus cannot be operating. The calculations allowed us to discover an unprecedented mechanism composed of four main steps as follows: (i) activation of the C(sp3)–H bond, (ii) oxidative addition, (iii) reductive elimination and (iv) regeneration of the active catalyst. After completion of step (i) via the CMD mechanism, the oxidative addition commences with an X ligand transfer from the iodine(iii) reagent (ArIX2) to Pd(ii) to form a square pyramidal complex in which an iodonium occupies the apical position. Interestingly, a simple isomerization of the resultant five-coordinate complex triggers the Pd(ii) oxidation. Accordingly, the movement of the ligand trans to the Pd–C(sp3) bond to the apical position promotes the electron transfer from Pd(ii) to iodine(iii), resulting in the reduction of iodine(iii) concomitant with the ejection of the second X ligand as a free anion. The ensuing Pd(iv) complex then undergoes the C–O reductive elimination by nucleophilic attack of the solvent (alcohol) on the sp3 carbon via an outer-sphere SN2 mechanism assisted by the X− anion. Noteworthy, starting from the five coordinate complex, the oxidative addition and reductive elimination processes occur with a very low activation barrier (ΔG‡ 0–6 kcal mol−1). The strong coordination of the alkoxylated product to the Pd(ii) centre causes the regeneration of the active catalyst, i.e. step (iv), to be considerably endergonic, leading to subsequent catalytic cycles to proceed with a much higher activation barrier than the first cycle. We also found that although, in most cases, the alkoxylation reactions proceed via a Pd(ii)–Pd(iv)–Pd(ii) catalytic cycle, the other alternative in which the oxidation state of the Pd(ii) centre remains unchanged during the catalysis could be operative, depending on the nature of the organic substrate.This work uses DFT calculations to explore Pd(ii)-catalysed iodine(iii)-mediated alkoxylation of unactivated C(sp3)–H bonds and reveals how important the isomerization is in triggering the oxidative addition of ArIX2 to Pd(ii). 相似文献
153.
Ali Keivanloo Mohammad BakheradBahram Bahramian Samaneh Baratnia 《Tetrahedron letters》2011,52(13):1498-1502
Silica-supported zinc bromide (ZnBr2/SiO2) is an efficient heterogeneous catalyst for the rapid synthesis of ynones by cross-coupling of acid chlorides with terminal alkynes in good to excellent yields under solvent-free conditions at room temperature. 相似文献
154.
A dehydroascorbic acid capped magnetite (DHAA-Fe3O4) catalyst is prepared and used for the one-pot synthesis of α-aminonitriles and α-aminophosphonates. Different derivatives of these compounds are synthesized in good yields. 相似文献