Krchnák Viktor, Moellmann Ute, Dahse Hans-Martin, Miller Marvin J
Department of Chemistry and Biochemistry, 251 Nieuwland Science Hall, University of Notre Dame, Notre Dame, Indiana 46556, USA.
J Comb Chem. 2008 Jan-Feb;10(1):94-103. doi: 10.1021/cc700140h. Epub 2007 Dec 8.
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.
制备了聚合物负载的酰基亚硝基亲双烯体，并将其用于与多种双烯体的杂环狄尔斯-阿尔德（HDA）反应。瞬态酰基亚硝基亲双烯体由固定化的异羟肟酸酯原位制备，这些异羟肟酸酯通过几种可被不同裂解试剂裂解的连接基连接到固体载体上，并用于合成N-未取代和N-衍生化的HDA加合物。使用模型化合物来（i）优化固相HDA反应的条件，（ii）评估与各种双烯体反应的结果，（iii）比较双烯体的相对反应活性，以及（iv）评估HDA加合物对通常用于固相合成的裂解条件的稳定性。将裂解产物进行生物学测定，并报告结果。随附的论文重点关注互补的芳基亚硝基HDA反应，其中包括对两种HDA反应的比较。
