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Enhancing the scope of the Diels-Alder reaction through isonitrile chemistry: emergence of a new class of acyl-activated dienophiles.

ABSTRACT: ?,?-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 ?,?-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.

SUBMITTER: Townsend SD

PROVIDER: S-EPMC3396883 | biostudies-literature | 2012 Jun

REPOSITORIES: biostudies-literature

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Enhancing the scope of the Diels-Alder reaction through isonitrile chemistry: emergence of a new class of acyl-activated dienophiles.

Townsend Steven D SD Wu Xiangyang X Danishefsky Samuel J SJ

Journal of the American Chemical Society 20120618 25

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 mo ...[more]

PMID: 22708980

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