A series of 3-allenyl benzo[b]thiophenes were synthesized through a gold(I)-catalyzed domino reaction. The process consists in 5-endo-dig cyclization with C−S bond formation and consecutive S-to-C propargyl migration via [3,3]-sigmatropic Claisen rearrangement. With aryl substituents on both triple bonds the substrate, subsequent intramolecular hydroarylation formed allenyl system led to 3-inde...

The conversion of geranyl pyrophosphate to (-)-endo-fenchol is considered to proceed by the initial isomerization of the substrate to (-)-(3R)-linalyl pyrophosphate and the subsequent cyclization of this bound intermediate. Incubation of (1R)-[2-14C,1-3H]- and (1S)-[2-14C,1-3H]geranyl pyrophosphate with a preparation of (-)-endo-fenchol cyclase (synthase) from common fennel (Foeniculum vulgare)...

The major toxaphene metabolites in sediment and soils (2-exo,3-endo,6-exo,8,9,10-hexachlorobornane [B6-923] and 2-endo,3-exo,5-endo,6-exo,8,9,10-heptachlorobornane [B7-1001]) were incubated with the isolated gram-negative bacterium Dehalospirillum multivorans. Within 14 d, biotransformation of B7-1001 was nearly quantitative, resulting in two penta- and six hexachlorobornanes, as well as one un...

The design, synthesis, and biological evaluation of irciniastatin A (1) analogues, achieved by removal of three synthetically challenging structural units, as well as by functional group manipulation of the C(11) substituent of both irciniastatins A and B (1 and 2), has been achieved. To this end, we first designed a convergent synthetic route toward the diminutive analogue (+)-C(8)-desmethoxy-...

The electronic and geometric structures of endo,endo-tetracyclo[4.2.1.1.0] dodeca-4,9-diene(TTDD) molecule have been investigated by ab initio and DFT/B3LYP methods with the 6-31G* and 6-311G* basis sets. The double bonds of TTDD molecule have been endo-pyramidalized. The structure of π-orbitals and their mutual interactions for TTDD molecule have been investigated. The cationic intermediates a...