Overhauser DNP and EPR in a Mobile Setup: Influence of Magnetic Field Inhomogeneity

Power-dependent Overhauser dynamic nuclear polarization (DNP) enhancements and continuous-wave electron paramagnetic resonance (EPR) spectra of nitroxide radicals were measured in the magnetic field of a mobile Halbach-array permanent magnet and compared with results from a commercially available electromagnet. DNP saturation factors for varying microwave power were obtained from both measurement series and used to investigate how the increased magnetic field inhomogeneity present in the Halbach magnet affects the saturation efficiency. An EPR detection system was designed to allow continuous-wave EPR measurements at microwave power up to 20?W. Our results show that despite the lower magnetic field homogeneity, a Halbach-array magnet can be used for EPR and DNP-enhanced nuclear magnetic resonance of high quality providing almost the same performance as a more homogeneous electromagnet.     

Enzyme-Catalyzed Synthesis of O-Glycopeptide Building Blocks

Abstract

In 1988, MOSBACH et aL¹ reported the synthesis of a-D-mannopyranosy1-L-serine and Q -D-N-acetylgalactosamino-L-serine by reversing the hydrolytic activity of a -mannosidase from jack beans and a -N-acetylgalactosaminidase from beef liver, respectively. The yields in these equilibrium-controlled syntheses² using high concentrations of monosaccharide and serine were highly dependent on the enzyme concentration and ranged from 5 to 10 percent in both cases.     

Synthesis and characterization of polymer linked copper(I) bis(N‐heterocyclic carbene) mechanocatalysts

In this paper, the synthesis and characterization of a series of latent polymeric bis(N‐heterocyclic carbene) (NHC) copper(I) complexes is reported, which can be activated for the copper(I)‐catalyzed azide/alkyne cycloaddition (CuAAC) via ultrasound. To prove the influence of chain length and nature of the polymer towards the activation, poly(isobutylene) (PIB), poly(styrene) (PS) and poly(tetrahydrofuran) (PTHF) are synthesized via living polymerization techniques (LCCP, ATRP, CROP) obtaining different chain lengths (from 2500 to 9000 g/mol), followed by quaternization with N‐methylimidazole, generating the corresponding N‐methylimidazolium‐telechelic polymers. The deprotonation of these macroligands via strong bases like sodium tert‐butoxide (NaO^tBu) or potassium hexamethyldisilazide (KHMDS) yields the free N‐heterocyclic carbenes (NHCs), which are used to coordinate to tetrakis(acetonitrile)copper(I) hexafluorophosphate, forming the final polymer‐based mono‐ and bis(N‐methylimidazole‐2‐ylidene) copper(I)X complexes. The structural proof of these complexes is accomplished via ¹H‐NMR spectroscopy, MALDI‐TOF‐MS and GPC‐techniques. The activation of the copper(I) biscarbene catalysts by ultrasound is studied by GPC, revealing the cleavage of one shielding NHC‐ligand. The initial catalytic latency and the via ultrasound introduced catalytic activation is successfully demonstrated monitoring a CuAAC “click” reaction of benzyl azide and phenylacetylene by in situ ¹H‐NMR spectroscopy introducing thus “click” conversions up to 97%. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3893–3907     

Pd‐Catalyzed Ring Assembly by Vinylation and Intramolecular Heck Coupling: A Versatile Strategy Towards Functionalized Azadibenzocyclooctynes

A new modular approach based on Pd‐catalyzed C? C bond formation is presented for the assembly of a benzannulated azocine scaffold, the key intermediate in the synthesis of functionalized azadibenzocyclooctynes (aza‐DIBOs). The intramolecular ring‐closing Heck coupling was investigated by variation of the C? X bond. The reaction rate is limited by the initial oxidative addition step and the regiochemistry strongly depends on the auxiliary phosphine. Under optimized conditions, the 8‐endo regioisomer was obtained in 71 % yield over two steps (with no protecting group chemistry) or in one pot, inclusive of C? N bond formation. The practical generation of the octyne triple bond of a prototypical N‐benzoyl aza‐DIBO, without the need for chromatographic purification, is also described. The structural features, including those of the ring‐strained cyclic octyne, were elucidated by NMR spectroscopy and X‐ray crystallographic analysis. The high reactivity of the N‐benzoyl aza‐DIBO synthesized is demonstrated in a strain‐promoted azide–alkyne cycloaddition reaction with an alkyl azide (k=0.38 M ^?1 s^?1).     

Heterocyclic analogs of xanthiones: 5,6‐fused 3‐methyl‐1‐phenylpyrano[2,3‐c]pyrazol‐4(1H) thiones—synthesis and NMR (1H, 13C, 15N) data

Various [5,6]pyrano[2,3‐c]pyrazol‐4(1H)‐thiones were synthesized in high yields by treatment of the corresponding [5,6]pyrano[2,3‐c]pyrazol‐4(1H)‐ones with Lawesson's reagent. Detailed NMR spectroscopic studies were undertaken of the title compounds. Complete and unambiguous assignment of chemical shifts (¹H, ¹³C, ¹⁵N) and coupling constants (¹H,¹H; ¹³C,¹H) was achieved by the combined application of various one‐ and two‐dimensional (1D and 2D) NMR spectroscopic techniques. Unequivocal mapping of most ¹³C,¹H spin coupling constants is accomplished by 2D (δ, J) long‐range INEPT spectra with selective excitation. Copyright © 2010 John Wiley & Sons, Ltd.