Synthesis of Elusive Chloropnictenium Ions

This work describes the synthesis and full characterization of elusive chloropnictenium ion salts of the type [^RAr*N(SiMe)ECl][A] (^RAr*=2,6‐(CHPh₂)‐4‐R‐C₆H₂, R=Me, tBu; E=Sb, Bi; A^?=GaCl₄, Al(OCH(CF₃)₂)₄). In these species the cation is significantly stabilized by weak arene interactions to flanking phenyl groups of the ^RAr* moiety. In this context the bonding situation has been studied by computational means and the reactivity towards the Lewis base 4‐dimethylaminopyridine (dmap) was investigated.     

Selective Benzylic CH-Borylations by Tandem Cobalt Catalysis

Metal-catalyzed C?H activations are environmentally and economically attractive synthetic strategies for the construction of functional molecules as they obviate the need for pre-functionalized substrates and minimize waste generation. Great challenges reside in the control of selectivities, the utilization of unbiased hydrocarbons, and the operation of atom-economical dehydrocoupling mechanisms. An especially mild borylation of benzylic CH bonds was developed with the ligand-free pre-catalyst Co[N(SiMe₃)₂]₂ and the bench-stable and inexpensive borylation reagent B₂pin₂ that produces H₂ as the only by-product. A full set of kinetic, spectroscopic, and preparative mechanistic studies are indicative of a tandem catalysis mechanism of CH-borylation and dehydrocoupling via molecular Co^I catalysts.     

A cationic cysteine-hydrazide as an enrichment tool for the mass spectrometric characterization of bacterial free oligosaccharides

In Campylobacterales and related ε-proteobacteria with N-linked glycosylation (NLG) pathways, free oligosaccharides (fOS) are released into the periplasmic space from lipid-linked precursors by the bacterial oligosaccharyltransferase (PglB). This hydrolysis results in the same molecular structure as the oligosaccharide that is transferred to a protein to be glycosylated. This allowed for the general elucidation of the fOS-branched structures and monosaccharides from a number of species using standard enrichment and mass spectrometry methods. To aid characterization of fOS, hydrazide chemistry has often been used for chemical modification of the reducing part of oligosaccharides resulting in better selectivity and sensitivity in mass spectrometry; however, the removal of the unreacted reagents used for the modification often causes the loss of the sample. Here, we develop a more robust method for fOS purification and characterize glycostructures using complementary tandem mass spectrometry (MS/MS) analysis. A cationic cysteine hydrazide derivative was synthesized to selectively isolate fOS from periplasmic fractions of bacteria. The cysteine hydrazide nicotinamide (Cyhn) probe possesses both thiol and cationic moieties. The former enables reversible conjugation to a thiol-activated solid support, while the latter improves the ionization signal during MS analysis. This enrichment was validated on the well-studied Campylobacter jejuni by identifying fOS from the periplasmic extracts. Using complementary MS/MS analysis, we approximated data of a known structure of the fOS from Campylobacter concisus. This versatile enrichment technique allows for the exploration of a diversity of protein glycosylation pathways.     

Calcium Hydride Reactivity: Formation of an Anionic N-Heterocyclic Olefin Ligand

An anionic N-heterocyclic olefin ligand was serendipitously obtained by reaction of an amidinate calcium hydride complex with 1,3-dimethyl-2-methyleneimidazole (NHO). Instead of anticipated addition to the polarized C=CH₂ bond to form an unstabilized alkylcalcium complex, deprotonation of the NHO ligand in the backbone was observed. Preference for deprotonation versus addition is explained by loss of aromaticity in the latter conversion. Theoretical calculations demonstrate the substantially increased ylidic character of this anionic NHO ligand which, like N-heterocyclic dicarbenes, shows strong bifunctional coordination.