Gold(I)-Catalyzed Rautenstrauch/Hetero-Diels–Alder/Retro-aza-Michael Cascade Reaction for the Synthesis of α-Hydrazineyl-2-cyclopentenones

Abstract

A one-pot synthesis of ring-fused, α-hydrazineyl-2-cyclopentenone derivatives is achieved by a gold(I)-catalyzed Rautenstrauch/hetero Diels–Alder/ring opening tandem reaction of suitable propargyl esters. By mixing the latter with a dialkylazodicarboxylate in the presence of a gold(I) catalyst, the 1,2-acyloxy migration/cyclization process (Rautenstrauch reaction) leads to cyclopentadienyl ester intermediates which are trapped by the heterodienophile present in situ. This provides strained intermediates which spontaneously undergo highly regioselective ring opening by a retro aza-Michael reaction promoted by the gold(I) catalyst, eventually yielding the target compounds. Six- and seven-membered ring-fused cyclopentenones bearing a pendant α-hydrazineyl moiety can be obtained in moderate to excellent yield (50–98%) by this approach, with a minimal erosion of the initial optical purity when using enantioenriched substrates.