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11.
Prof. Dr. Jevgenij A. Raskatov Dr. Scott Virgil Dr. Hsiau-Wei Lee Dr. Lawrence M. Henling Ka Chan Ariel J. Kuhn Alejandro R. Foley 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(20):4467-4470
Methionine (Met) oxidation is an important biological redox node, with hundreds if not thousands of protein targets. The process yields methionine oxide (MetO). It renders the sulfur chiral, producing two distinct, diastereomerically related products. Despite the biological significance of Met oxidation, a reliable protocol to separate the resultant MetO diastereomers is currently lacking. This hampers our ability to make peptides and proteins that contain stereochemically defined MetO to then study their structural and functional properties. We have developed a facile method that uses supercritical CO2 chromatography and allows obtaining both diastereomers in purities exceeding 99 %. 1H NMR spectra were correlated with X-ray structural information. The stereochemical interconversion barrier at sulfur was calculated as 45.2 kcal mol−1, highlighting the remarkable stereochemical stability of MetO sulfur chirality. Our protocol should open the road to synthesis and study of a wide variety of stereochemically defined MetO-containing proteins and peptides. 相似文献
12.
Julia Leitl Dr. Andrew R. Jupp Dr. Evi R. M. Habraken Verena Streitferdt Dr. Peter Coburger Dr. Daniel J. Scott Prof. Dr. Ruth M. Gschwind Prof. Dr. Christian Müller Dr. J. Chris Slootweg Prof. Dr. Robert Wolf 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(35):7788-7800
Salt metathesis of 1-methyl-2,4,6-triphenylphosphacyclohexadienyl lithium and chlorobis(pentafluorophenyl)borane affords a 1-phospha-7-bora-norbornadiene derivative 2 . The C≡N triple bonds of nitriles insert into the P−B bond of 2 with concomitant C−B bond cleavage, whereas the C≡C bonds of phenylacetylenes react with 2 to form λ4-phosphabarrelenes. Even though 2 must formally be regarded as a classical Lewis adduct, the C≡N and C≡C activation processes observed (and the mild conditions under which they occur) are reminiscent of the reactivity of frustrated Lewis pairs. Indeed, NMR and computational studies give insight into the mechanism of the reactions and reveal the labile nature of the phosphorus–boron bond in 2 , which is also suggested by detailed NMR spectroscopic studies on this compound. Nitrile insertion is thus preceded by ring opening of the bicycle of 2 through P−B bond splitting with a low energy barrier. By contrast, the reaction with alkynes involves formation of a reactive zwitterionic methylphosphininium borate intermediate, which readily undergoes alkyne 1,4-addition. 相似文献
13.
Gilian T. Thomas Sofia Donnecke Prof. Irina Paci Prof. J. Scott McIndoe 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(54):12359-12362
Zeise's salt, [PtCl3(H2C=CH2)]−, is the oldest known organometallic complex, featuring ethylene strongly bound to a platinum salt. Many derivatives are known, but none involving dinitrogen, and indeed dinitrogen complexes are unknown for both platinum and palladium. Electrospray ionization mass spectrometry of K2[PtCl4] solutions generate strong ions corresponding to [PtCl3(N2)]−, the identity of which was confirmed through ion-mobility spectrometry and MS/MS experiments that proved it to be distinct from its isobaric counterparts [PtCl3(C2H4)]− and [PtCl3(CO)]−. Computational analysis established a gas-phase platinum–dinitrogen bond strength of 116 kJ mol−1, substantially weaker than the ethylene and carbon monoxide analogues but stronger than for polar solvents such as water, methanol and dimethylformamide, and strong enough that the calculated N−N bond length of 1.119 Å represents weakening to a degree typical of isolated dinitrogen complexes. 相似文献
14.
Dr. Thomas G. Hayhow Rachel E. A. Borrows Dr. Coura R. Diène Gary Fairley Dr. Charlene Fallan Dr. Shaun M. Fillery Dr. James S. Scott Dr. David W. Watson 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(70):16818-16823
A palladium-catalysed Buchwald–Hartwig amination for lenalidomide-derived aryl bromides was optimised using high throughput experimentation (HTE). The substrate scope of the optimised conditions was evaluated for a range of alkyl- and aryl- amines and functionalised aryl bromides. The methodology allows access to new cereblon-based bifunctional proteolysis targeting chimeras with a reduced step count and improved yields. 相似文献
15.
Mossel and Ross raised the question of when a random coloring of a graph can be reconstructed from local information, namely, the colorings (with multiplicity) of balls of given radius. In this article, we are concerned with random 2-colorings of the vertices of the -dimensional hypercube, or equivalently random Boolean functions. In the worst case, balls of diameter are required to reconstruct. However, the situation for random colorings is dramatically different: we show that almost every 2-coloring can be reconstructed from the multiset of colorings of balls of radius 2. Furthermore, we show that for , almost every -coloring can be reconstructed from the multiset of colorings of 1-balls. 相似文献
16.
Dr. Samuel C. Scott Dr. Jamie A. Cadge Grace K. Boden Prof. John F. Bower Dr. Christopher A. Russell 《Angewandte Chemie (International ed. in English)》2023,62(23):e202301526
We describe a AuI complex of a hemi-labile (C^N) N-heterocyclic carbene ligand that is able to mediate oxidative addition of aryl iodides. Detailed computational and experimental investigations have been undertaken to verify and rationalize the oxidative addition process. Application of this initiation mode has resulted in the first examples of “exogenous oxidant-free” AuI/AuIII catalyzed 1,2-oxyarylations of ethylene and propylene. These demanding yet powerful processes establish these commodity chemicals as nucleophilic-electrophilic building blocks in catalytic reaction design. 相似文献
17.
Chathuranga S. L. Rathnamalala Selena Hernandez Dr. Melissa Y. Lucero Chelsea B. Swartchick Dr. Abdul Kalam Shaik Prof. Dr. Nathan I. Hammer Amanda K. East Prof. Dr. Steven R. Gwaltney Prof. Dr. Jefferson Chan Prof. Dr. Colleen N. Scott 《Angewandte Chemie (International ed. in English)》2023,62(13):e202214855
Shortwave infrared (SWIR) dyes are characterized by their ability to absorb light from 900 to 1400 nm, which is ideal for deep tissue imaging owing to minimized light scattering and interference from endogenous pigments. An approach to access such molecules is to tune the photophysical properties of known near-infrared dyes. Herein, we report the development of a series of easily accessible (three steps) SWIR xanthene dyes based on a dibenzazepine donor conjugated to thiophene ( SCR-1 ), thienothiophene ( SCR-2 ), or bithiophene ( SCR-3 ). We leverage the fact that SCR-1 undergoes a bathochromic shift when aggregated for in vivo studies by developing a ratiometric nanoparticle for NO ( rNP-NO ), which we employed to successfully visualize pathological levels of nitric oxide in a drug-induced liver injury model via deep tissue SWIR photoacoustic (PA) imaging. Our work demonstrates how easily this dye series can be utilized as a component in nanosensor designs for imaging studies. 相似文献
18.
Anna G. Scott Diogo Alves Galico Isabel Bogacz Paul H. Oyala Junko Yano Elizaveta A. Suturina Muralee Murugesu Theodor Agapie 《Angewandte Chemie (International ed. in English)》2023,62(49):e202313880
Atomically defined large metal clusters have applications in new reaction development and preparation of materials with tailored properties. Expanding the synthetic toolbox for reactive high nuclearity metal complexes, we report a new class of Fe clusters, Tp*4W4Fe13S12 , displaying a Fe13 core with M−M bonds that has precedent only in main group and late metal chemistry. M13 clusters with closed shell electron configurations can show significant stability and have been classified as superatoms. In contrast, Tp*4W4Fe13S12 displays a large spin ground state of S=13. This compound performs small molecule activations involving the transfer of up to 12 electrons resulting in significant cluster rearrangements. 相似文献
19.
New cage models (MeAlO)n(Me3Al)m (n=16, m=6 or 7) isomeric with previously reported sheet models for the principle activator found in hydrolytic MAO (h-MAO) are compared at M06-2X and MN15 levels of theory using density functional theory with respect to their thermodynamic stability. Reactivity of the neutrals or corresponding anions with formula [(MeAlO)16(Me3Al)6Me]− towards chlorination, and loss of Me3Al is explored while reactivity of the neutrals towards formation of contact- and outer-sphere ion pairs from Cp2ZrMe2 and Cp2ZrMeCl is examined. The results suggest on balance that a cage model for this activator is less consistent with experiment than an isomeric sheet model, although the latter are more stable based on free energy. 相似文献
20.
Dr. Ross McLellan Maria A. Palacios Dr. Christine M. Beavers Dr. Simon J. Teat Dr. Stergios Piligkos Prof. Euan K. Brechin Dr. Scott J. Dalgarno 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(7):2804-2812
Methylene‐bridged calix[4]arenes have emerged as extremely versatile ligand supports in the formation of new polymetallic clusters possessing fascinating magnetic properties. Metal ion binding rules established for this building block allow one to partially rationalise the complex assembly process. The ability to covalently link calix[4]arenes at the methylene bridge provides significantly improved control over the introduction of different metal centres to resulting cluster motifs. Clusters assembled from bis‐calix[4]arenes and transition metal ions or 3d‐4f combinations display characteristic features of the analogous calix[4]arene supported clusters, thereby demonstrating an enhanced and rational approach towards the targeted synthesis of complex and challenging structures. 相似文献