Capturing fleeting intermediates in a catalytic C–H amination reaction cycle

We have applied an ambient ionization technique, desorption electrospray ionization MS, to identify transient reactive species of an archetypal C–H amination reaction catalyzed by a dirhodium tetracarboxylate complex. Using this analytical method, we have detected previously proposed short-lived rea...

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Published inProceedings of the National Academy of Sciences - PNAS Vol. 109; no. 45; pp. 18295 - 18299
Main Authors Perry, Richard H, Cahill, Thomas J, Roizen, Jennifer L, Du Bois, Justin, Zare, Richard N
Format Journal Article
LanguageEnglish
Published United States National Academy of Sciences 06.11.2012
National Acad Sciences
Subjects
Adducts
Amination
Analytical chemistry
analytical methods
Atoms
Atoms & subatomic particles
Catalysis
Chemical reactions
Desorption
Hydrocarbons
hydrogen
Ionization
Isotopes
Mass spectra
Mass spectrometry
Mass spectroscopy
oxidants
Oxidation
Physical Sciences
Sulfonamides
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Summary:We have applied an ambient ionization technique, desorption electrospray ionization MS, to identify transient reactive species of an archetypal C–H amination reaction catalyzed by a dirhodium tetracarboxylate complex. Using this analytical method, we have detected previously proposed short-lived reaction intermediates, including two nitrenoid complexes that differ in oxidation state. Our findings suggest that an Rh-nitrene oxidant can react with hydrocarbon substrates through a hydrogen atom abstraction pathway and raise the intriguing possibility that two catalytic C–H amination pathways may be operative in a typical bulk solution reaction. As highlighted by these results, desorption electrospray ionization MS should have broad applicability for the mechanistic study of catalytic processes.
Bibliography:http://dx.doi.org/10.1073/pnas.1207600109
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Author contributions: R.H.P., T.J.C., J.L.R., J.D.B., and R.N.Z. designed research; R.H.P. and T.J.C. performed research; J.L.R. contributed new reagents/analytic tools; R.H.P., T.J.C., and J.L.R. analyzed data; and R.H.P., T.J.C., J.L.R., J.D.B., and R.N.Z. wrote the paper.
1R.H.P. and T.J.C. contributed equally to this work.
Edited* by Robert G. Bergman, University of California, Berkeley, CA, and approved September 21, 2012 (received for review May 4, 2012)
ISSN:0027-8424
1091-6490
DOI:10.1073/pnas.1207600109