Danishefsky's diene

Abstract

(A) The enantioselective hetero-Diels-Alder reaction of Danishefskys diene with benzaldehyde has been achieved both experimentally and theoretically, incorporating a series of α, α, α′, α′- tetraaryl-1,3-dioxolane-4,5-dimethanol (TADDOL) derivatives as catalysts, affording 2-phenyl-2,3-dihydro-4H-pyran-4-one (1).3 (figure presented) (B) After acetylation, condensation between Danishefskys diene and benzoquinone afforded a stable methoxytriacetoxydihydronaphthalene intermediate 2, which was subsequently transformed into the regiospecific 7-naphthylboronic acid 3 by the Snieckus DOM protocol.4 (figure presented) (C) Mandai and co-workers delineated the reaction of Danishefskys diene with aryl-/alkyl-substituted aldimine catalyzed by silver in the presence of a ligand leading to the formation of pyridinone 4.5 (figure presented) (D) Alaimo and co-workers have designed domino reactions where the nitroarene reduction by indium(0) generates an amine to which addition of an aldehyde followed by Danishefskys diene provides access to dihydropyridin-4-ones 5. The yields are comparable or superior to the reported stepwise reactions. 6 (figure presented) (figure presented) (E) The hetero-DielsAlder reaction between glyceraldehyde acetonide and the Danishefskys diene formed one of the key steps in the enantioselective formal total synthesis of the cytotoxic macrolide (+)-aspergillide C (10). 7 (figure presented) (F) Tropones reacting with Danishefskys diene served one of the important steps in a multistep synthesis of polycyclic compounds 12. 8 (figure presented) (G) Chaladaj et al. presented a simple and efficient synthetic route to chiral cis-6-substituted 2-(2-hydroxyethyl)-5,6-dihydro-2H-pyrans, a versatile chiral building block, by performing three key transformations: enantioselective hetero-DielsAlder reaction of an aldehyde with Danishefskys diene, selective reduction of the carbonyl function, and Claisen or related rearrangement. The synthetic utility of this methodology was illustrated by the total synthesis of antibiotic ()-centolobine 14. 9. © Thieme Stuttgart New York.