The intramolecular Rauhut-Currier reaction creates a carbon-carbon bond between two tethered Michael acceptors. Previous asymmetric versions have relied on 1,4-additions of chiral nucleophilic catalysts. Herein, we investigate a novel strategy that involves the formation of electron rich dienamines as key intermediates. Our methodology provides an efficient entry to the iridoid framework.

We disclose herein a highly enantioselective de novo-synthesis of chiral 1-cyclopentenyl-α-keto esters starting from a simple bis-silyl-1,3-dienediolate and α,β-unsaturated aldehydes via a domino vinylogous Michael-intramolecular Knoevenagel-type condensation. The cyclopentenes proved to be highly versatile and were readily converted into various structural motifs.

Exhaustive Michael-type alkylations of amines and ammonia with azoalkenes (generated from α-halohydrazones) were demonstrated as an efficient approach to poly(hydrazonomethyl)amines - a novel class of polynitrogen ligands. An intramolecular cyclotrimerization of C=N bonds in tris(hydrazonomethyl)amine to the respective 1,4,6,10-tetraazaadamantane derivative was demonstrated.

Hydrogenated [60]fullerenes, prepared from [60]fullerene and sodium borohydride, react with alkylidenecyanoacetates [RCH=CCN(CO2Et): R 1⁄4 C6H5 (2a), 4-CH3O–C6H4 (2b), 4-NO2–C6H4 (2c), H (2d)] and alkylidenemalononitriles [RCH=C(CN)2 : R 1⁄4 C6H5 (2e), 4-CH3O–C6H4 (2f), 4-NO2–C6H4 (2g), 4-(CH3)2N–C6H4 (2h)] under basic conditions to afford cyclopentenylfullerenes 3. No multi-cycloaddition produ...

Total syntheses of the potent neurotoxins, environmental hazards, and biochemical probes anatoxin-a and homoanatoxin have been achieved from a common intermediate using a combined two-directional synthesis-tandem reaction strategy which includes key advances in oxidative desymmetrisation, tandem Michael-intramolecular Mannich cyclisations and a new method for deprotection of N-tosyl anatoxin-a.