The Mechanism of Tröger's Base Formation Probed by Electrospray Ionization Mass Spectrometry

Abella, Carlos A. M.; Benassi, Mario; Santos, Leonardo S.; Eberlin, Marcos N.; Coelho, Fernando

doi:10.1021/jo062556w

Cited by 37 publications

(22 citation statements)

References 57 publications

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“…ESI‐MS has been shown to be a useful technique for carrying out mechanistic studies33 because it transfers ions directly from the solution to the gas phase smoothly and efficiently (no or little dissociation), thereby providing snapshots of the ion composition of the reaction solutions. We have used this technique extensively to investigate the mechanisms of some major reactions 34–36…”

Section: Resultsmentioning

confidence: 99%

Chemoselective Aromatic Azido Reduction with Concomitant Aliphatic Azide Employing Al/Gd Triflates/NaI and ESI‐MS Mechanistic Studies

Kamal

Markandeya

Shankaraiah

et al. 2009

Chemistry A European J

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Aluminium and gadolinium triflates catalyze the chemoselective reduction of aromatic azides to the corresponding amines in combination with sodium iodide. This mild chemoselective method has been applied to the synthesis of various aryl amines, C2-azido-substituted pyrrolo[2,1-c][1,4]benzodiazepines, and fused[2,1-b]quinazolinones by an intramolecular azido reduction tandem cyclization reaction. Interestingly, this methodology selectively reduces aryl azides with enhanced yields and proceeds in shorter reaction times than previous strategies. The mechanistic aspects have been investigated and the intermediates associated with this selective transformation have been intercepted and characterized by online monitoring of the reaction by ESI-MS.

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Section: Resultsmentioning

confidence: 99%

Chemoselective Aromatic Azido Reduction with Concomitant Aliphatic Azide Employing Al/Gd Triflates/NaI and ESI‐MS Mechanistic Studies

Kamal

Markandeya

Shankaraiah

et al. 2009

Chemistry A European J

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“…In a recent work, Eberlin and Coelho monitored the condensations between p ‐toluidine and formaldehyde or hexamethylenetetramine in situ in TFA by electrospray ionization mass and tandem mass spectrometry [ESI‐MS/MS] 33. This technique permitted the detection and characterization of – along with iminium ion 4 (Scheme ) – the oxidized forms of two of the intermediates suggested by Wagner ([ 6 –H] and [ 10 –H], Figure 4).…”

Section: Synthesis Of Tröger's Base and Analoguesmentioning

confidence: 99%

Prevention of postoperative adhesion formation by individual and combined administration of 4 per cent icodextrin and dimetindene maleate (Br J Surg 2009; 96: 1476–1483)

Watkins¹

2010

British Journal of Surgery

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“…In trying to elucidate major mechanistic aspects, different methylene sources as well as different anilines have been used by Abella et al [72] to form Tr€ ogers bases. In trying to elucidate major mechanistic aspects, different methylene sources as well as different anilines have been used by Abella et al [72] to form Tr€ ogers bases.…”

Section: Tr€ Ogers Basesmentioning

confidence: 99%

Organic Reaction Studies by ESI‐MS

Nachtigall

Eberlin

2009

Reactive Intermediates

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IntroductionReactions are the heart and soul of chemistry. Therefore chemists, to effectively control and improve their chemical reactions, need to know the mechanistic details by which these usually sophisticated, multistep and multicomponent processes with many intermediates and transient species proceed. The tremendous success and rapid broad use of electrospray ionization mass spectrometry (ESI-MS) [1] results mainly from its ability to transfer, in a gentle and efficient way, ions of many types, charge states and nearly unlimited masses from the real-world environment of reaction solutions directly to the diluted gas phase and to characterize these intact and isolated gaseous ions according to their masses and connectivities with the outstanding speed, sensitivity and selectivity that only mass spectrometry is able to provide. ESI-MS (for ion detection and mass and isotopic pattern determination) as well as its tandem version ESI-MS(/MS) (for structural investigation) has therefore established itself as the principal technique to study reaction mechanisms of organic reactions in solution. ESI can fish, rapidly and efficiently, reactants, intermediates and products (either ionic species or molecules in ionic forms) and transfer them to mass spectrometers (leaving behind the solvent molecules and counter ions) to measure their masses and access their structures and intrinsic reactivities using tandem MS/MS experiments. Continuous on-line monitoring of organic reactions of many types by ESI-MS(/MS) ion fishing (Figure 3.1) provides instantaneous and comprehensive snapshots of the ionic composition and thus permits organic chemists to follow how these reactions progress as a function of time and reaction conditions, whereas the high sensitivity and speed of ESI-MS allow even transient (low concentrations for short times) intermediates to be detected and characterized. The intrinsic reactivity of each key gaseous species fished by ESI can also be further investigated via ESI-MS(/MS) experiments in the search for the most intrinsically active species via gas-phase ion/ molecule reactions in which solvent and counter-ion effects are absent. Therefore, the ability to fish ions (or neutral, zwitterionic, or radical species in ionic forms such as protonated, deprotonated, or cationized or anionized molecules) provides a detailed j63 64j 3 Organic Reaction Studies by ESI-MS R 1 OH Scheme 3.2 Currently accepted catalytic cycle for the MBH reaction. 3.2 Reaction Mechanisms j65 66j 3 Organic Reaction Studies by ESI-MS À , CF 3 CO 2 À ). 68j 3 Organic Reaction Studies by ESI-MS 70j 3 Organic Reaction Studies by ESI-MS 98j 3 Organic Reaction Studies by ESI-MS

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The Mechanism of Tröger's Base Formation Probed by Electrospray Ionization Mass Spectrometry

Cited by 37 publications

References 57 publications

Chemoselective Aromatic Azido Reduction with Concomitant Aliphatic Azide Employing Al/Gd Triflates/NaI and ESI‐MS Mechanistic Studies

Chemoselective Aromatic Azido Reduction with Concomitant Aliphatic Azide Employing Al/Gd Triflates/NaI and ESI‐MS Mechanistic Studies

Prevention of postoperative adhesion formation by individual and combined administration of 4 per cent icodextrin and dimetindene maleate (Br J Surg 2009; 96: 1476–1483)

Organic Reaction Studies by ESI‐MS

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