Part I. Diels-Alder reactions of heterocyclic azadienes: Studies toward the total synthesis of P-3A, total synthesis of desacetamido P-3A, and desacetamidopyrimidoblamic acid. Part II. Diels-Alder reactions of oxabutadienes: Synthetic studies toward the disaccharide moiety of bleomycin A2
Abstract
Studies toward the enantioselective total synthesis of P-3A, a natural product isolated during the biosynthetic studies of bleomycins, consisting a pyrimidine nucleus commonly occurring in the bleomycin antibiotics, are described. The total syntheses of desacetamido P-3A and desacetamidopyrimidoblamic acid are detailed and the syntheses are based on the application of an inverse electron demand Diels-Alder reaction of 2,4,6-tris(ethoxycarbonyl)-1,3,5-triazine in a 1,3,5-triazine $\to$ pyrimidine strategy for the efficient preparation of the pyrimidine moiety of the bleomycin antitumor antibiotics. The scope of the (4+2) cycloaddition reaction of 2,4,6-tris(ethoxycarbonyl)- and 2,4,6-tris(methylthio)-1,3,5-triazine is detailed. Results of the synthetic studies toward the disaccharide moiety of bleomycin A$\sb2$ through oxabutadienes Diels-Alder reactions are also described.
Degree
Ph.D.
Advisors
Boger, Purdue University.
Subject Area
Organic chemistry
Off-Campus Purdue Users:
To access this dissertation, please log in to our
proxy server.