NDLI: An exploratory and mechanistic study of the defluorination of an (aminofluorophenyl)oxazolidinone: SN1(Ar*) vs. SR+N1(Ar*) mechanism

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An exploratory and mechanistic study of the defluorination of an (aminofluorophenyl)oxazolidinone: S_N1(Ar) vs. S_R⁺N1(Ar) mechanism

Content Provider	Royal Society of Chemistry (RSC)
Author	Tilocca, Fedele Protti, Stefano Albini, Angelo Merli, Daniele Fasani, Elisa
Copyright Year	2008
Abstract	The morpholinofluorophenyloxazolidinone 1 (the antibacterial drug linezolid) is found to undergo reductive defluorination upon irradiation in water (Φ 0.33), in some of the products accompanied by the simultaneous oxidative degradation of the morpholine side chain. In the presence of chloride, iodide and pyrrole, the fluorine is substituted by these groups (with pyrrole, in position 2). The defluorination is less efficient in methanol and mainly leads to reduction (Φ 0.053). These data can be accommodated through two different mechanisms, viz. either C–F bond heterolysis to give a phenyl cation [SN1(Ar)], or ionization to give a radical cation [SR+N1(Ar)]. Steady-state and time resolved data have been gathered for clarifying this issue. It is found that, indeed, ionization of 1 is efficient and proceeds from the singlet, but leads to no irreversible change. On the contrary, triplet 31 (lifetime 0.5 μs in MeOH, <0.1 μs in water) fragments and gives the corresponding triplet phenyl cation. The last intermediate explains well the observed hydrogen abstraction both inter- (from the solvent, when this is reducing) and intramolecularly (from the morpholine group), as well as addition to a charged anion or to a neutral π nucleophile such as pyrrole. The rationalization is supported by the study of some related molecules. Thus, the only photochemical reaction from the non fluorinated analogue of linezolid (that ionizes just as 1) is an inefficient degradation of the morpholine chain (Φ 0.001), while a simple model such as N-(2-fluorophenyl)morpholine undergoes photosolvolysis in water and is not trapped by pyrrole.
Starting Page	4634
Ending Page	4642
Page Count	9
File Format	HTM / HTML PDF
ISSN	14770520
Volume Number	6
Issue Number	24
Journal	Organic & Biomolecular Chemistry
DOI	10.1039/b812372a
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Fluorine Hydrogen Haloalkane Ion Heterolysis (chemistry) Phenyl group Mechanistic organic photochemistry Morpholine Chloride MeOH Ionization Pyrrole Solvent Methanol Substitution reaction Nucleophile
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry Biochemistry Physical and Theoretical Chemistry

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