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91.
Herein, we report a practical synthesis of 2-D-l-tryptophan via sequential Ir-catalyzed CH borylation, and Ir-catalyzed C-2-deborylative deuteration steps. In this synthetic sequence, deprotection of the Boc and methyl ester groups proved challenging, due to replacement of deuterium with hydrogen. However, mild deprotection conditions were developed to avoid this D/H scrambling. Further, 2-D-L-Tryptophan is stable in many buffers used for biological studies. 相似文献
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Ryan J. Schwamm Mathew D. Anker Matthias Lein Martyn P. Coles 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(5):1503-1507
The potassium aluminyl complex K[Al(NONAr)] (NON=NONAr=[O(SiMe2NAr)2]2?, Ar=2,6‐iPr2C6H3) reacts with 1,3,5,7‐cyclooctatetraene (COT) to give K[Al(NONAr)(COT)]. The COT‐ligand is present in the asymmetric unit as a planar μ2‐η2:η8‐bridge between Al and K, with additional K???π‐aryl interactions to neighboring molecules that generate a helical chain. DFT calculations indicate significant aromatic character, consistent with reduction to [COT]2?. Addition of 18‐crown‐6 causes a rearrangement of the C8‐carbocycle to form the isomeric 9‐aluminabicyclo[4.2.1]nona‐2,4,7‐triene anion. 相似文献
95.
Kelly R. Morrison Ryan A. Allen Kevin P.C. Minbiole William M. Wuest 《Tetrahedron letters》2019,60(37):150935
Quaternary ammonium compounds (QACs) are a class of antimicrobials that have been around for over a century; nevertheless, they have found continued renewal in the structures to which they can be appended. Ranging from antimicrobial polymers to adding novel modes of action to existing antibiotics, QACs have found ongoing use due to their potent properties. However, resistance against QACs has begun to emerge, and the mechanism of resistance is still only partially understood. In this review, we aim to summarize the current state of the field and what is known about the mechanisms of resistance so that the QACs of the future can be designed to be evermore efficacious and utilized to unearth the remaining mysteries that surround bacteria’s resistance to them. 相似文献
96.
Victor Adebomi Ryan D. Cohen Rachel Wills Holland Andrew Hays Chavers Gary E. Martin Monika Raj 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(52):19249-19256
Here, we report a novel “CyClick” strategy for the macrocyclization of peptides that works in an exclusively intramolecular fashion thereby precluding the formation of dimers and oligomers via intermolecular reactions. The CyClick chemistry is highly chemoselective for the N‐terminus of the peptide with a C‐terminal aldehyde. In this protocol, the peptide conformation internally directs activation of the backbone amide bond and thereby facilitates formation of a stable 4‐imidazolidinone‐fused cyclic peptide with high diastereoselectivity (>99 %). This method is tolerant to a variety of peptide aldehydes and has been applied for the synthesis of 12‐ to 23‐membered rings with varying amino acid compositions in one pot under mild reaction conditions. The reaction generated peptide macrocycles featuring a 4‐imidazolidinone in their scaffolds, which acts as an endocyclic control element that promotes intramolecular hydrogen bonding and leads to macrocycles with conformationally rigid turn structures. 相似文献
97.
Micropatterning of the vapochromic charge-transfer salt, [Pt(CNC6H4C10H21)4][Pd(CN)4], on transparent platforms yields transmissive chemoresponsive diffraction gratings. Exposure of the gratings to volatile organic compounds (VOCs) such as chloroform and methanol leads to VOC uptake by the porous material comprising the grating lattice or framework, and a change in the material's complex refractive index, ?. The index change is accompanied by a change in the degree of index contrast between the lattice and the surrounding medium (in this case, air), and a change in the diffraction efficiency of the grating. When a monochromatic light source that is not absorbed by the lattice material is employed as a probe beam, only changes in the real component of ? are sensed. Under these conditions, the grating behaves as a nonselective, but moderately sensitive, sensor for those VOCs capable of permeating the porous lattice material. When a probe color is shifted to a wavelength coincident with the vapochromic charge-transfer transition of the lattice material, the sensor response is selectively amplified by up to 3.5 orders of magnitude, resulting in greatly enhanced sensitivity and some degree of chemical specificity. On the basis of studies at four probe wavelengths, the amplification effect is dominated by resonant changes in the imaginary component of the refractive index. The observed wavelength- and analyte-dependent amplification effects are quantitatively well described by a model that combines a Kramers-Kronig analysis with an effective-medium treatment of dielectric effects. 相似文献
98.
Cobb SL Deng H Hamilton JT McGlinchey RP O'Hagan D 《Chemical communications (Cambridge, England)》2004,(5):592-593
5'-Fluoro-5'-deoxy-D-ribose-1-phosphate (FDRP) is identified as a biosynthetic intermediate during fluorometabolite biosynthesis in Streptomyces cattleya. 相似文献
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100.
Susann Paul W. Bernd Schweizer Graham Rugg Hans Martin Senn Ryan Gilmour 《Tetrahedron》2013,69(27-28):5647-5659
Herein, we report the synthesis and X-ray structural analysis of a collection of fluorinated metal N-heterocyclic carbenes (Ag, Au, Pd, Rh, Ir) and their precursor salts. The common structural feature of these species is a flanking fluoroethyl group, which is either freely rotating or embedded within a bicyclic framework. Solid state analysis confirmed a gauche conformational preference in all cases with the fluorine adopting a syn clinal arrangement (?[NCCF]~60°) with respect to the triazolium nitrogen at the vicinal position of the NHC. A density functional theory analysis was employed to quantify these effects and evaluate the influence of electronic modulation of the carbenic carbon [(CN+); neutral carbene (C:); metal-bound carbene (CM)], on the relative gauche/anti preference, thus highlighting the potential of this conformational phenomenon as a useful molecular design strategy for controlling the topology of organometallic complexes. 相似文献