ABSTRACT
The asymmetric synthesis of warfarin in microdroplets and thin films generated by an electrospray ionization (ESI) source is reported. This is one of the first examples of an enantioselective organocatalyzed reaction in electrosprayed confined volumes. The optimal conditions in terms of system setting were established for this reaction.
ABSTRACT
The esterification reaction of different amino acids with methanol catalyzed by H2SO4 was first studied in the small volume of thin films generated by ESI microdroplet deposition. The reaction is promoted by the pneumatic spray of the ESI source and reaches its maximum efficiency at a thin film temperature of 70 °C. Selective esterification of the COOH moiety was demonstrated. Microdroplet size and thin film volume and lifetime are critical parameters that influenced the reaction outcome. As expected, l-tyrosine and l-phenylalanine having aromatic side chain substituents were the most reactive amino acids, reaching absolute yields of around 40-50%. The amino acid esterification catalyzed by H2SO4 in a thin film occurs under synthetic conditions in which the same reaction in the bulk is not observed.
ABSTRACT
The Maillard reaction kinetics in the confined volume of the thin film produced by ESI microdroplet deposition was studied by mass spectrometry. The almost exclusive formation of the Amadori product from the reaction of D-xylose and D-glucose toward L-glycine and L-lysine was demonstrated. The thin film Maillard reaction occurred at a mild synthetic condition under which the same process in solution was not observed. The comparison of the thin film kinetics with that of the reaction performed in solution showed strong thin film rate acceleration factors.
Subject(s)
Maillard Reaction , Xylose , Glucose , Glycine/chemistry , Lysine/analysis , Xylose/chemistryABSTRACT
RATIONALE: The occurrence of N-heterocyclic carbenes in imidazolium-based ionic liquids has long been discussed, but no spectroscopic evidence has been reported yet due to their transient nature. The insertion of an ionizable acid group into the cation scaffold of an ionic liquid which acts as a charge tag allows for the direct detection of free carbenes by mass spectrometry. METHODS: Three different Brønsted acidic ionic liquids were synthesized: 1-methyl-3-carboxymethylimidazolium chloride (MAICl), 1-methyl-3-carboxymethylimidazolium acetate (MAIAc) and the corresponding 2-(3-methyl-1H-imidazol-3-ium-1-yl)acetate zwitterion (MAI - H). The speciation of these compounds was then analysed by electrospray ionization ion-trap mass spectrometry in the negative ion mode. RESULTS: The C2-H deprotonation of the imidazolium cation leading to the formation of the corresponding carbene is highly affected by the basic properties of the counter-anion. In the case of MAICl and MAI - H ionic liquids, no charged species corresponding to the free N-heterocyclic carbene was detected. On the contrary, in the presence of a sufficiently basic anion, such as acetate of MAIAc ionic liquid, an intense signal related to the free carbenic species was observed without the addition of an external base. CONCLUSIONS: In situ formation of free N-heterocyclic carbenes from Brønsted acidic ionic liquids was demonstrated, highlighting the crucial role of anion basicity in promoting the C2-H proton abstraction from imidazolium cations with a carboxylic side chain.
ABSTRACT
Thin films derived by the deposition of charged microdroplets generated in the ESI source of a mass spectrometer act as highly concentrated reaction vessels in which the final products of an ion-molecule reaction can be isolated by their precipitation onto a solid surface under ambient conditions. In this study, the ESI Z-spray source supplied to a Q-TOF Ultima mass spectrometer was used to investigate the d-fructose acid-catalyzed reactions by microdroplets deposition onto a stainless-steel target surface. High conversion ratios of d-fructose into 5-hydroxymethylfuraldehyde (5-HMF), 5-methoxymethylfuraldehyde (5-MMF), and difructrose anhydrides (DFAs) were obtained with HCl and KHSO4 as metal-free catalysts by using synthetic conditions under which the same products in bulk are not formed. Furthermore, the reaction outcome was found to be highly sensitive to the catalyst and the solvent employed as well as to the ESI source parameters influencing the thin film formation from microdroplets deposition onto the solid surface.
