Chandra Kanta De, Eric G. Klauber, and Daniel Seidel*
J. Am.Chem.Soc. ASAP
11/13/2009
• used for kineCc resoluCon and desymmetrizaCon processes • enanCoselecCve acyl transfer pathways
• III could be a beJer acylaCng agent than II,
• proper choice of X‐ and reacCon medium : decrease solubility of II over III
new concept for asymmetric nucleophilic catalysis : kineCc resoluCon of primary amines.
De, C.K.; Klauber, E.G.; Seidel, D. J. Am.Chem.Soc. 2009, 131, XXXX
Fu, G. C.; Arai, S.; Bellemin-Laponnaz, S. Angew. Chem. Int. Ed. 2001, 40, 234-236.
Fu, G. C.; Arp, F. O. J. Am. Chem. Soc 2006, 128, 14264-14265.
Mioskowski, C.; Srseniyadis, S.; Valleix, A.; Wagner, A. Angew. Chem. Int. Ed. 2004, 43, 3314-3317.
List, B.; Hoffmann, S.; Nicoletti, M. J. Am. Chem. Soc 2006, 128, 13074-13075.
0.01 M concentraCon providing the best s‐factor 20 mol % of DMAP improved s‐factor to 10
Lowering of both catalysts: s‐factors slightly reduced
De, C.K.; Klauber, E.G.; Seidel, D. J. Am.Chem.Soc. 2009, 131, XXXX
Only DMAP:No effect on reacCon rate no DMAP : significant
amounts of enanCoenriched product
Other HB catalysts:inferior results
De, C.K.; Klauber, E.G.; Seidel, D. J. Am.Chem.Soc. 2009, 131, XXXX
in the absence of DMAP : HB acCvaCon of the anhydride
In the presence of DMAP: B dominates
De, C.K.; Klauber, E.G.; Seidel, D. J. Am.Chem.Soc. 2009, 131, XXXX
e poor :beJer s‐factor