Solid-supported nitroso hetero Diels-Alder reactions. 1. Acylnitroso dienophiles: scope and limitations.
Polymer-supported acylnitroso dienophiles were prepared and used in hetero Diels-Alder (HDA) reactions with a variety of dienes. The transient acylnitroso dienophiles were prepared in situ from immobilized hydroxamates, which were attached to solid supports via several linkers each cleavable by different cleavage reagents, and served for the synthesis of both N-unsubstituted and N-derivatized HDA adducts. Model compounds were used to (i) optimize reaction conditions for solid-supported HDA reactions, (ii) evaluate the outcome of the reactions with various dienes, (iii) compare relative reactivities of dienes, and (iv) assess the stability of HDA adducts toward cleavage conditions typically used in solid-phase syntheses. Cleaved products were submitted to biological assays, and the results are reported. The accompanying paper, focused on complementary arylnitroso HDA reactions, includes a comparison of both HDA reactions.
Krchnák
Viktor
V
Department of Chemistry and Biochemistry, 251 Nieuwland Science Hall, University of Notre Dame, Notre Dame, Indiana 46556, USA. vkrchnak@nd.edu
Moellmann
Ute
U
Dahse
Hans-Martin
HM
Miller
Marvin J
MJ
D000215:Acylation; D020650:Combinatorial Chemistry Techniques / Q000379:methods*; D005240:Feasibility Studies; D006571:Heterocyclic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D006877:Hydroxamic Acids / Q000737:chemistry; D015394:Molecular Structure; D009603:Nitroso Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D010078:Oxazines / Q000737:chemistry; D010084:Oxidation-Reduction; D011108:Polymers / Q000737:chemistry*
D006571:Heterocyclic Compounds; D006877:Hydroxamic Acids; D009603:Nitroso Compounds; D010078:Oxazines; D011108:Polymers