Microstructural Analysis of Benzoxazine Cationic Ring-Opening Polymerization Pathways.

Herein, an evaluation of the initial step of benzoxazine polymerization is presented by mass spectrometry, with a focus on differentiating the phenoxy and phenolic products formed by distinct pathways of the cationic ring opening polymerization (ROP) mechanism of polybenzoxazine formation. The use of infrared multiple photon dissociation (IRMPD) and ion mobility spectrometry (IMS) techniques allows for differentiation of the two pathways and provides valuable insights into the ROP mechanism. The results suggest that type I pathway is favored in the initial stages of the reaction yielding the phenoxy product, while type II product should be observed at later stages when the phenoxy product would interconvert to the most stable type II phenolic product. Overall, the findings presented here provide important information on the initial step of the benzoxazine polymerization, allowing the development of optimal polymerization conditions and represents a way to evaluate other multifunctional polymerization processes.

Trichloro(Dinitrogen)Platinate(II).

Zeise's salt, [PtCl3 (H2 C=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 (C2 H4 )]- 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 Šrepresents weakening to a degree typical of isolated dinitrogen complexes.

Diastereoselective dearomative cycloaddition of bicyclobutanes with pyridinium ylides: a modular approach to multisubstituted azabicyclo[3.1.1]heptanes.

Diastereoselective (3+3) cycloaddition between bicyclobutanes and pyridinium ylides forms azabicyclo[3.1.1]heptanes via pyridine dearomatization. These reactions proceed under ambient conditions with no need for photochemistry or catalysis, and tolerate a wide range of functional gorups. The resulting multicyclic ring systems have diverse synthetic handles for further transformations, making them potentially valuable for the design of Csp3-rich drug candidates. These include semi-reduction of the dihydropyridine, and diastereoselective photochemical skeletal rearrangement to give a tetrasubstituted cyclobutane.

Reductive 1,2-Arylation of Isatins.

We report an intermolecular Ni-catalyzed reductive coupling of aryl iodides and isatins to form 3-hydroxyoxindoles. In contrast to common metal-mediated methods, sec-butanol is used as a mild stoichiometric reductant resulting in benign waste products. This formal 1,2-addition reaction is facilitated by a 1,5-diaza-3,7-diphosphacyclooctane (P2N2) ligand. Two Ni(0)-P2N2 species are prepared and found to be catalytically active, supporting a mechanistic hypothesis that this reaction proceeds by a modified carbonyl-Heck-type pathway.

A mechanistic investigation of the Pd-catalyzed cross-coupling between N-tosylhydrazones and aryl halides.

The cross-coupling of N-tosylhydrazones and aryl halides forms carbon-carbon bonds, producing 1,1-disubstituted alkenes. Though it has proven extremely useful in several fields of chemistry, its mechanism remains experimentally unexplored. Combining benchtop NMR and real-time mass spectrometry afforded the ability to monitor the catalytic intermediates as well as the rate of product formation.

Step-by-step real time monitoring of a catalytic amination reaction.

The multiple reaction monitoring mode of a triple quadrupole mass spectrometer is used to examine the Buchwald-Hartwig amination reaction at 0.1% catalyst loading in real-time using sequential addition of reagents to probe the individual steps in the cycle. This is a powerful new method for probing reactions under realistic conditions.