264621-69-4Relevant articles and documents
Visible-Light-Mediated Liberation and In Situ Conversion of Fluorophosgene
Petzold, Daniel,Nitschke, Philipp,Brandl, Fabian,Scheidler, Veronica,Dick, Bernhard,Gschwind, Ruth M.,K?nig, Burkhard
supporting information, p. 361 - 366 (2018/11/23)
The first example for the photocatalytic generation of a highly electrophilic intermediate that is not based on radical reactivity is reported. The single-electron reduction of bench-stable and commercially available 4-(trifluoromethoxy)benzonitrile by an organic photosensitizer leads to its fragmentation into fluorophosgene and benzonitrile. The in situ generated fluorophosgene was used for the preparation of carbonates, carbamates, and urea derivatives in moderate to excellent yields via an intramolecular cyclization reaction. Transient spectroscopic investigations suggest the formation of a catalyst charge-transfer complex-dimer as the catalytic active species. Fluorophosgene as a highly reactive intermediate, was indirectly detected via its next downstream carbonyl fluoride intermediate by NMR. Furthermore, detailed NMR analyses provided a comprehensive reaction mechanism including a water dependent off-cycle equilibrium.
Carbon dioxide as a carbonylating agent in the synthesis of 2-oxazolidinones, 2-oxazinones, and cyclic ureas: Scope and limitations
Paz, Jairo,Perez-Balado, Carlos,Iglesias, Beatriz,Munoz, Luis
supporting information; experimental part, p. 3037 - 3046 (2010/07/15)
Carbon dioxide can be used as a convenient carbonylating agent in the synthesis of 2-oxazolidinones, 2-oxazinones, and cyclic ureas. The transient carbamate anion generated by treating a primary or secondary amine group in basic media can be activated with phosphorylating agents such as Diphenylphosphoryl azide (DPPA) and Diphenyl chlorophosphate (DPPCl) but also with other types of electrophiles such as SOCl2, TsCl, or AcCl. The intramolecular trapping of the activated carbamate by a hydroxyl group leads to the formation of 2-oxazolidinones or 2-oxazinones in good to excellent yields. This methodology was successfully applied to the synthesis of cyclic ureas up to 7-membered rings from the corresponding diamines.
Asymmetric synthesis of amlnocyclopropanes and N-cyclopropylamino alcohols through direct amidocyclopropanation of alkenes using chiral organozinc carbenoids
Begis, Guillaume,Cladingboel, David E.,Jerome, Laure,Motherwell, William B.,Sheppard, Tom D.
experimental part, p. 1532 - 1548 (2009/09/08)
Chiral N-(diethoxymethyl)oxazolidinones, prepared from the corresponding oxazolidinones by heating in trielhyl orthoformate, can be used as organozinc carbenoid precursors for the direct enantioselective amidocyclopropanation of alkenes. The reaction is successful with a wide range of oxazolidinones and alkenes and proceeds with moderate to excellent yield and stereoselectivity. In most cases the trans/exo amidocyclopropane product, is favoured, although certain cyclic alkenes such as indene favour the formation of the endo cyclopropane. The products can be readily elaborated to produce cyclopropylamino alcohols and amino acids. Wiley-VCH Verlag GmbH & Co. KGaA.
Carbonylation with CO2 and phosphorus electrophiles: A convenient method for the synthesis of 2-oxazolidinones from 1,2-amino alcohols
Paz, Jairo,Pérez-Balado, Carlos,Iglesias, Beatriz,Mu?oz, Luis
scheme or table, p. 395 - 398 (2009/08/09)
2-Oxazolidinones were prepared in good yields from 1,2-amino alcohols and CO2 in the presence of tetramethyl-phenylguanidine (PhTMG) as a base and a variety of phosphorus electrophiles under mild conditions. This procedure is advantageous over previous methodologies and relies on a novel carbonylation procedure that utilizes nontoxic CO2 and phosphorus electrophiles. Georg Thieme Verlag Stuttgart.
