Synthesis of oxazolidinones: rhodium-catalyzed C-H amination of N-mesyloxycarbamates.

@article{Lebel2017SynthesisOO,
  title={Synthesis of oxazolidinones: rhodium-catalyzed C-H amination of N-mesyloxycarbamates.},
  author={H. Lebel and Laura Mamani Laparra and M. Khalifa and C. Trudel and Cl{\'e}ment Audubert and Mathieu Szponarski and C{\'e}dric Dicaire Leduc and Emna Azek and M. Ernzerhof},
  journal={Organic \& biomolecular chemistry},
  year={2017},
  volume={15 19},
  pages={
          4144-4158
        }
}
N-Mesyloxycarbamates undergo intramolecular C-H amination reactions to afford oxazolidinones in good to excellent yields in the presence of rhodium(ii) carboxylate catalysts. The reaction is performed under green conditions and potassium carbonate is used, forming biodegradable potassium mesylate as a reaction by-product. This method enables the production of electron-rich, electron-deficient, aromatic and heteroaromatic oxazolidinones in good to excellent yields. Conformationally restricted… Expand
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References

SHOWING 1-10 OF 86 REFERENCES
Stereoselective synthesis of chiral sulfilimines from N-mesyloxycarbamates: metal-nitrenes versus metal-nitrenoids species.
TLDR
The synthesis of a variety of chiral sulfilimines and sulfoximines is described, and it is believed that the bispyridinium salt played the role of a phase transfer catalyst, influencing both the yield and the diastereoselectivity of the reaction. Expand
N-tosyloxycarbamates as reagents in rhodium-catalyzed C-H amination reactions.
Metal nitrenes for use in C-H insertion reactions were obtained from N-tosyloxycarbamates in the presence of an inorganic base and a rhodium(II) dimer complex catalyst. The C-H amination reactionExpand
N-Boc Amines to Oxazolidinones via Pd(II)/Bis-sulfoxide/Brønsted Acid Co-Catalyzed Allylic C–H Oxidation
TLDR
Mechanistic studies suggest the role of the phosphoric acid is to furnish a Pd(II)bis-sulfoxide phosphate catalyst that promotes allylic C–H cleavage and π-allylPd functionalization with a weak, aprotic oxygen nucleophile and to assist in catalyst regeneration. Expand
Enzymatic C(sp3)-H Amination: P450-Catalyzed Conversion of Carbonazidates into Oxazolidinones
TLDR
Improved active-site variants of the bacterial P450 CYP102A1 could be identified to mediate the aminofunctionalization of two terpene natural products with high regio- and stereoselectivity. Expand
Rhodium(II)-catalyzed aziridination of allyl-substituted sulfonamides and carbamates.
TLDR
The expected aziridine was not observed, but rather simultaneous spirocyclization of C(3) and stereoselective syn-acylation at C(2) occurred to give compound 41, whose structure was unequivocally established by an X-ray crystallographic study. Expand
Solvent enhancement of reaction selectivity: a unique property of cationic chiral dirhodium carboxamidates.
TLDR
The enhancement of reaction rates and selectivities with cationic chiral dirhodium(II,III) carboxamidates in toluene suggests broad applications for them in Lewis acid catalyzed reactions. Expand
N-tosyloxycarbamates as a source of metal nitrenes: rhodium-catalyzed C-H insertion and aziridination reactions.
TLDR
The rhodium-catalyzed decomposition of N-tosyloxycarbamates to generate metal nitrenes which undergo intramolecular C-H insertion or aziridination reaction is described, as both reactions are stereospecific. Expand
Novel stereoselective synthesis of functionalized oxazolidinones from chiral aziridines.
Enantiomerically pure N-(R)-alpha-methylbenzyl-4(R)-(chloromethyl)oxazolidinones (4R)-5a-k were synthesized in one step and high yields from various aziridine-2-methanols (S)-2a-k by intramolecularExpand
Cycloaddition of tertiary aziridines and carbon dioxide using a recyclable organocatalyst, 1,3-di-tert-butylimidazolium-2-carboxylate: straightforward access to 3-substituted 2-oxazolidones
Imidazolium-2-carboxylates derived from N-heterocyclic carbenes (NHCs) and CO2 serve as efficient catalysts for CO2-carboxylation of tertiary aziridines bearing various substituents such as halogens,Expand
Carbon dioxide as a carbonylating agent in the synthesis of 2-oxazolidinones, 2-oxazinones, and cyclic ureas: scope and limitations.
TLDR
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 in the synthesis of cyclic ureas up to 7-membered rings from the corresponding diamines. Expand
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