Tunable Gold-catalyzed Reactions of Propargyl Alcohols and Aryl Nucleophiles.

Gold-catalyzed transformations of 1,3-diarylpropargyl alcohols and various aryl nucleophiles were studied. Selective tunable synthetic methods were developed for 1,1,3-triarylallenes, diaryl-indenes and tetraaryl-allyl target products by C3 nucleophilic substitution and subsequent intra- or intermolecular hydroarylation, respectively. The reactions were scoped with regards to gold(I)/(III) catalysts, solvent, temperature, and electronic and steric effects of both the diarylpropargyl alcohol and the aryl nucleophiles.

Rapid and mild synthesis of Au-NHC complexes in a simple two-phase flow reactor.

We describe a simple two-phase flow reactor which allows for the rapid synthesis of several Au(i)-NHC complexes in high yields (>88%), under mild conditions, and with minimal workup. Translation of the standard weak base method to a two-phase flow reaction prevents the common problem of decomposition to Au(0). The reaction can be scaled up more than ten-fold without loss in conversion efficiency.

Studies on gold(I) and gold(III) alcohol functionalised NHC complexes.

Five pairs of novel chiral alcohol functionalised gold(i) and gold(iii) NHC complexes derived from chiral amino alcohols, were synthesized and characterised (NMR, IR, HRMS). Single crystal X-ray diffraction data of gold(i) and gold(iii) complexes are reported and discussed. The chiral imidazolium preligands were readily synthesized via the oxalamides, subsequent reduction and final orthoformate condensation.

Studies on gold-nitrone systems.

A series of novel Au(i)-nitrone complexes with specific catalytic properties were prepared. Furthermore, Au(i)- and Au(iii)-oxadiazole complexes were formed by a novel Au-generated nitrile-nitrone [3 + 2] cycloaddition, and the crystal structures of Au(i)-nitrones as well as the Au(i)- and Au(iii)-oxadiazole complexes were studied (X-ray). A useful one-pot Au(iii)-mediated cycloaddition method was developed for the formation of a number of dihydro-1,2,4-oxadiazoles, involving in situ formation of Au(iii)-oxadiazole complexes.

Gold(I)-Catalyzed [2 + 2 + 2] Cyclotrimerization of 1,3-Diarylpropargyl Acetals.

A gold-nitrone catalyzed [2 + 2 + 2] cyclotrimerization of 1,3-diarylpropargyl acetals into cyclohexylidene products (up to 74% yield) is reported. The trimerization is proposed to proceed through allenic intermediates via gold-catalyzed 1,3-alkoxy rearrangement. The presence of catalytic amounts of different nitrones, tuning of the Au(I) catalyst activity, was essential for controlled regio-/chemoselective cyclotrimerization.