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991.
Conrad T. Pfeiffer Justin D. Northrup Jae Eun Cheong Melody A. Pham Matthew F.L. Parker Christian E. Schafmeister 《Tetrahedron letters》2018,59(30):2884-2888
Spiroligomers are a class of peptidomimetics that connect interchangeable, stereochemically pure, cyclic monomers through pairs of amide bonds to form diketopiperazines between the monomers. This enables them to adopt predictable and programmable structure due to the rigidity of the final molecule. We present a new method for the solid phase synthesis of highly functionalized spiroligomers that incorporates the use of the p-nitrobenzyloxycarbonyl (pNZ) as a temporary amine protecting group and the pentafluorophenyl ester for monomer activation. This new method allows for the synthesis of spiroligomers with higher purity and increased yields when compared to previous methods. This improved method of synthesis of functionalized spiroligomers will facilitate the development of applications as catalysts, therapeutics and membrane channels. 相似文献
992.
993.
Matthew J. O'Neill Tim Riesebeck Josep Cornella 《Angewandte Chemie (International ed. in English)》2018,57(29):9103-9107
Presented herein is a general protocol for the alkylation of simple aryl fluorides with unbiased secondary Grignard reagents by means of nickel catalysis. This study revealed a general Thorpe–Ingold effect in the ligand backbone which confers a high degree of selectivity for the secondary carbon center in the C?C coupling event. This protocol is characterized by mild reaction conditions, robustness, and simplicity. Both electron‐rich and electron‐deficient aryl fluorides are suitable candidates in this transformation. Equally amenable are a variety of heterocycles, permitting the coupling without over alkylation at the electrophilic sites. 相似文献
994.
The β‐Agostic Structure in (C5Me5)2Sc(CH2CH3): Solid‐State NMR Studies of (C5Me5)2Sc−R (R=Me,Ph, Et) 下载免费PDF全文
Damien B. Culver Winn Huynh Dr. Hosein Tafazolian Dr. Ta‐Chung Ong Prof. Dr. Matthew P. Conley 《Angewandte Chemie (International ed. in English)》2018,57(30):9520-9523
Multinuclear solid‐state NMR studies of Cp*2Sc?R (Cp*=pentamethylcyclopentadienyl; R=Me, Ph, Et) and DFT calculations show that the Sc?Et complex contains a β‐CH agostic interaction. The static central transition 45Sc NMR spectra show that the quadrupolar coupling constants (Cq) follow the trend of Ph≈Me>Et, indicating that the Sc?R bond is different in Cp*2Sc?Et compared to the methyl and phenyl complexes. Analysis of the chemical shift tensor (CST) shows that the deshielding experienced by Cβ in Sc?CH2CH3 is related to coupling between the filled σC‐C orbital and the vacant orbital. 相似文献
995.
Satrajit Chakrabarty Matthew J. DiTucci Giel Berden Jos Oomens Evan R. Williams 《Journal of the American Society for Mass Spectrometry》2018,29(9):1835-1847
Gas phase infrared dissociation spectra of the radical cation, deprotonated and protonated forms of the hormone melatonin, and its complexes with alkali (Li+, Na+, and K+) and alkaline earth metal ions (Mg2+, Ca2+, and Sr2+) are measured in the spectral range 800–1800 cm?1. Minimum energy geometries calculated at the B3LYP/LACVP++** level are used to assign structural motifs to absorption bands in the experimental spectra. The melatonin anion is deprotonated at the indole-N. The indole-C linking the amide chain is the most favored protonation site. Comparisons between the experimental and calculated spectra for alkali and alkaline earth metal ion complexes reveal that the metal ions interact similarly with the amide and methoxy oxygen atoms. The amide I band undergoes a red shift with increasing charge density of the metal ion and the amide II band shows a concomitant blue shift. Another binding motif in which the metal ions interact with the amide-O and the π-electron cloud of the aromatic group is identified but is higher in energy by at least 18 kJ/mol. Melatonin is deprotonated at the amide-N with Mg2+ and the metal ion coordinates to the amide-N and an indole-C or the methoxy-O. These results provide information about the intrinsic binding of metal ions to melatonin and combined with future studies on solvated melatonin-metal ion complexes may help elucidate the solvent effects on metal ion binding in solution and the biochemistry of melatonin. These results also serve as benchmarks for future theoretical studies on melatonin-metal ion interactions. 相似文献
996.
Matthew B. O’Rourke Benjamin B. A. Raymond Steven P. Djordjevic Matthew P. Padula 《Journal of the American Society for Mass Spectrometry》2018,29(3):512-515
Tissue imaging using matrix assisted laser desorption/ionization mass spectrometry (MALDI-MS) is a well-established technique that, in recent years, has seen wider adoption and novel application. Applications such imaging mass spectrometry (IMS) and biotyping are beginning to gain greater exposure and use; however, with limitations in optimization methods, producing the best result often relies on the ability to customize the physical characteristics of the instrumentation, a task that is challenging for most mass spectrometry laboratories. With this in mind, we have described the effect of making simple adjustments to the laser optics at the final collimating lens area, to adjust the laser beam size and shape in order to allow greater customization of the instrument for improving techniques such as IMS. We have therefore been able to demonstrate that improvements can be made without requiring the help of an electrical engineer or external funding in a way that only costs a small amount of time. 相似文献
997.
Dr. Erli Lu Josef T. Boronski Dr. Matthew Gregson Dr. Ashley J. Wooles Prof. Stephen T. Liddle 《Angewandte Chemie (International ed. in English)》2018,57(19):5506-5511
Unprecedented silyl‐phosphino‐carbene complexes of uranium(IV) are presented, where before all covalent actinide–carbon double bonds were stabilised by phosphorus(V) substituents or restricted to matrix isolation experiments. Conversion of [U(BIPMTMS)(Cl)(μ‐Cl)2Li(THF)2] ( 1 , BIPMTMS=C(PPh2NSiMe3)2) into [U(BIPMTMS)(Cl){CH(Ph)(SiMe3)}] ( 2 ), and addition of [Li{CH(SiMe3)(PPh2)}(THF)]/Me2NCH2CH2NMe2 (TMEDA) gave [U{C(SiMe3)(PPh2)}(BIPMTMS)(μ‐Cl)Li(TMEDA)(μ‐TMEDA)0.5]2 ( 3 ) by α‐hydrogen abstraction. Addition of 2,2,2‐cryptand or two equivalents of 4‐N,N‐dimethylaminopyridine (DMAP) to 3 gave [U{C(SiMe3)(PPh2)}(BIPMTMS)(Cl)][Li(2,2,2‐cryptand)] ( 4 ) or [U{C(SiMe3)(PPh2)}(BIPMTMS)(DMAP)2] ( 5 ). The characterisation data for 3 – 5 suggest that whilst there is evidence for 3‐centre P?C?U π‐bonding character, the U=C double bond component is dominant in each case. These U=C bonds are the closest to a true uranium alkylidene yet outside of matrix isolation experiments. 相似文献
998.
Selective Reductive Elimination at Alkyl Palladium(IV) by Dissociative Ligand Ionization: Catalytic C(sp3)−H Amination to Azetidines 下载免费PDF全文
Manuel Nappi Chuan He William G. Whitehurst Ben G. N. Chappell Prof. Dr. Matthew J. Gaunt 《Angewandte Chemie (International ed. in English)》2018,57(12):3178-3182
A palladium(II)‐catalyzed γ‐C?H amination of cyclic alkyl amines to deliver highly substituted azetidines is reported. The use of a benziodoxole tosylate oxidant in combination with AgOAc was found to be crucial for controlling a selective reductive elimination pathway to the azetidines. The process is tolerant of a range of functional groups, including structural features derived from chiral α‐amino alcohols, and leads to the diastereoselective formation of enantiopure azetidines. 相似文献
999.
The Molecular Structure of gauche‐1,3‐Butadiene: Experimental Establishment of Non‐planarity 下载免费PDF全文
Dr. Joshua H. Baraban Dr. Marie‐Aline Martin‐Drumel P. Bryan Changala Dr. Sandra Eibenberger Dr. Matthew Nava Prof. David Patterson Prof. John F. Stanton Prof. G. Barney Ellison Dr. Michael C. McCarthy 《Angewandte Chemie (International ed. in English)》2018,57(7):1821-1825
The planarity of the second stable conformer of 1,3‐butadiene, the archetypal diene for the Diels–Alder reaction in which a planar conjugated diene and a dienophile combine to form a ring, is not established. The most recent high level calculations predicted the species to adopt a twisted, gauche structure owing to steric interactions between the inner terminal hydrogens rather than a planar, cis structure favored by the conjugation of the double bonds. The structure cis‐1,3‐butadiene is unambiguously confirmed experimentally to indeed be gauche with a substantial dihedral angle of 34°, in excellent agreement with theory. Observation of two tunneling components indicates that the molecule undergoes facile interconversion between two equivalent enantiomeric forms. Comparison of experimentally determined structures for gauche‐ and trans‐butadiene provides an opportunity to examine the effects of conjugation and steric interactions. 相似文献
1000.
Cover Picture: Controlled Expansion of a Strong‐Field Iron Nitride Cluster: Multi‐Site Ligand Substitution as a Strategy for Activating Interstitial Nitride Nucleophilicity (Angew. Chem. Int. Ed. 40/2018) 下载免费PDF全文