Enantioselective oxa-Diels-Alder Sequences of Dendralenes.

ABSTRACT: Diene-transmissive hetero-Diels-Alder sequences involving carbonyl dienophiles are reported for the first time. High enantioselectivities are achieved in the reaction of phenylglyoxal with a broad range of dendralene structures, through the optimization of a Pd²⁺ catalyst system. The initial catalyst-controlled enantioselective oxa-Diels-Alder (ODA) cycloaddition to a [3]dendralene generates a dihydropyran carrying a semicyclic diene. This participates in a subsequent catalyst or substrate-controlled Diels-Alder reaction to generate sp³ -rich fused polycyclic systems containing both heterocycles and carbocycles. Computational investigations reveal a concerted asynchronous mechanism. π-Complexation of a diene C=C bond to Pd²⁺ occurs in both the pre-transitio

SUBMITTER: Fan YM 

PROVIDER: S-EPMC9804868 | biostudies-literature | 2022 Sep

REPOSITORIES: biostudies-literature