The synthesis of enantiomerically pure, highly functionalized heterocycles: the products of amino acid based acylnitroso hetero Diels-Alder reactions.
The diastereoselectivities of several chiral acylnitroso dienophiles (9a-h, 12 and 15) derived from optically pure, N-protected alpha-amino hydroxamic acids (2a-h, 4 and 7) were determined in an intermolecular hetero Diels-Alder reaction with cyclopentadiene. The diastereomeric excesses ranged from 0 to 72%. Hydroxamic acids with polar functionality were examined extensively to determine the effect of hydrogen bonding on the cycloaddition. The largest increase in diastereoselectivity was observed with increasing the steric bulk at the alpha-position of the hydroxamic acids and not with potential hydrogen bonding interactions. The cycloadditions afforded synthetically useful quantities of functionally rich, enantiomerically pure heterocycles (10a-h, 11a-h, 13, 14, 16 and 17), which have been elaborated into a variety of biologically interesting products.
Department of Chemistry and Biochemistry, University of Notre Dame, Indiana 46556, USA.
P F
PF
Vogt
M J
MJ
Miller
M J
MJ
Mulvihill
S
S
Ramurthy
G C
GC
Savela
A R
AR
Ritter
D000596:Amino Acids / Q000737:chemistry*; D006571:Heterocyclic Compounds / Q000138:chemical synthesis*; D006877:Hydroxamic Acids / Q000737:chemistry; D009603:Nitroso Compounds / Q000737:chemistry*; D013237:Stereoisomerism
D000596:Amino Acids; D006571:Heterocyclic Compounds; D006877:Hydroxamic Acids; D009603:Nitroso Compounds