Technology Spotlights

Benzoyloxycarbamates for the Base-free, Intermolecular Aminohydroxylation Reaction


The widely used Sharpless aminohydroxylation and asymmetric aminohydroxylation (AA) reactions are effective, one-step procedures for the formation of a vicinal amino alcohol moiety from a simple alkene. The vicinal alcohols produced are found in many biologically active compounds.1 An alternative intermolecular method designed by Donohoe provides several useful additions to the field.2 Using novel benzoyloxycarbamates, researchers at IRL-GlycoSyn have fed back facets of Donohoe’s method into the original intermolecular process.3 This technology is robust, high-yielding and compatible with base-sensitive protecting groups such as Fmoc.



General Reaction Scheme

Ethyl- (AHR001), benzyl- (AHR002), tert-butyl- (AHR003), and fluorenylmethyl-(AHR004) 4-chlorobenzoyloxycarbamates, compounds 1-4 in the scheme above, are available as nitrogen-source reagents. These nitrogen-source reagents are stable, easily-handled solids that can be stored at room temperature.



Example Reaction



References

  1. Li, G.; Hubert. H,; Sharpless, K. B. Angew. Chem. Int. Ed. Engl. 1996, 35, 2813-2817 and references therein.
  2. (a) Donohoe, T. J.; Johnson, P. D.; Cowley, A.; Keenan, M. J. Am. Chem. Soc. 2002, 124, 12934-12935. (b) Donohoe, T.J.; Bataille, C.J.R.; Gattrell, W.; Kloesges, J.; Rossignol, E. Org. Lett, 2007, 9, 1725-1728.
  3. For complete scope and reaction details, please see: Harris, L.; Mee, S. P. H.; Furneaux, R. H.; Gainsford, G. J.; Luxenburger A. J. Org. Chem. 2011, 76, 358-372.