Tandem Au(III)-catalyzed heterocyclization/Nazarov cyclizations leading to substituted carbocycle fused furans are described. An interesting dichotomy of reaction pathways as a function of solvent, confirmed by the isolation and trapping of reaction intermediates, provided a basis for computational studies that supported the experimental findings.

Synthesis of substituted 1,3-dienes was achieved viagold(I)-catalyzed Claisen rearrangement of allenyl vinyl ethers. The N-heterocyclic carbenegold chloride catalyst (IPrAuCl) was superior in terms of activity and selectivity and afforded the 3,3-product in excellent yields. A proposed cation-π inter-action played a significant role in affecting the reaction rate.

An intermolecular Morita–Baylis–Hillman (MBH) reaction using dicobalthexacarbonyl complexed acetylenic acetals as the electrophile is reported. Employing BF3–OEt2 as the Lewis acid with a sulfide as the Lewis base MBH adducts were obtained.

The one-pot Darzens condensation of α,β-unsaturated aldehydes and ketones with enolates of an α-bromo ester or ketone is described.

Under trialkylphosphine catalyzed Morita–Baylis–Hillman reaction conditions, epoxides react with enones to give rise to homologous aldol adducts.

sp3 Hybridized electrophiles, never before used in the organomediated Morita–Baylis–Hillman reaction, now facilitate the formation of five- and six-membered enone cycloalkylation products.

The unprecedented reactivity of Co4(CO)12 with enynes under aqueous conditions, representing the development of a mild and simple aqueous-phase cobalt-catalyzed PK reaction protocol, is described herein.

Unusual Pd-catalyzed cyclizations of unsymmetrical allylic acetates, where the nucleophile is tethered to the central allyl carbon, are shown for the first time to be remarkably controlled by heteroatom-mediated preassociation of the reacting partners.

Tandem Au(III)-catalyzed heterocyclization/Nazarov cyclizations leading to substituted carbocycle fused furans are described. An interesting dichotomy of reaction pathways as a function of solvent, confirmed by the isolation and trapping of reaction intermediates, provided a basis for computational studies that supported the experimental findings.

Synthesis of substituted 1,3-dienes was achieved viagold(I)-catalyzed Claisen rearrangement of allenyl vinyl ethers. The N-heterocyclic carbenegold chloride catalyst (IPrAuCl) was superior in terms of activity and selectivity and afforded the 3,3-product in excellent yields. A proposed cation-π inter-action played a significant role in affecting the reaction rate.