Enhancing the scope of the Diels-Alder reaction through isonitrile chemistry: emergence of a new class of acyl-activated dienophiles.
α,β-Unsaturated imides, formylated at the nitrogen atom, comprise a new and valuable family of dienophiles for servicing Diels-Alder reactions. These systems are assembled through extension of recently discovered isonitrile chemistry to the domain of α,β-unsaturated acids. Cycloadditions are facilitated by Et(2)AlCl, presumably via chelation between the two carbonyl groups of the N-formyl amide. Applications of the isonitrile/Diels-Alder logic to the IMDA reaction, as well as methodologies to modify the N-formyl amide of the resultant cycloaddition product, are described. It is expected that this easily executed chemistry will provide a significant enhancement for application of Diels-Alder reactions to many synthetic targets.
Laboratory for Bioorganic Chemistry, Sloan-Kettering Institute for Cancer Research, 1275 York Avenue, New York, New York 10065, USA.
Steven D
SD
Townsend
Xiangyang
X
Wu
Samuel J
SJ
Danishefsky
D000215:Acylation; D000577:Amides / Q000737:chemistry; D015394:Molecular Structure; D009570:Nitriles / Q000737:chemistry*
D000577:Amides; D009570:Nitriles