The synthesis of a new type of Hoveyda-Grubbs 2(nd) generation catalyst bearing a modified N-heterocyclic carbene ligands is reported. The new catalyst contains an NHC ligand symmetrically substituted with chromanyl moieties. The complex was tested in model CM and RCM reactions. It showed very high activity in CM reactions with electron-deficient α,β-unsaturated compounds even at 0 °C. It was a...

The combination of the N-based pincer ligand PyBOX with Pt2+ leads to new catalysts for the enantioselective cycloisomerization of dienyl- and trienyl-ols. The mechanistic combination of electrophilic cyclization followed by rapid protodemetalation is surprising and leads to a powerful construct for developing new reactions.

Complexation of (tricarbonyl)iron to an acyclic diene serves to protect the ligand against oxidation, reduction and cycloaddition reactions while the steric bulk of this adjunct serves to direct the approach reagents to unsaturated groups attached to the diene onto the face opposite to iron. Furthermore, the Fe(CO)(3) moiety can serve to stabilize carbocation centers adjacent to the diene (i.e....

There are no data on the effects of different growth media on polyene-induced postantifungal effect (PAFE) in Candida species. Hence, the nystatin- and amphotericin B-induced PAFEs in six Candida species (26 isolates) grown in Sabouraud's dextrose broth (SAB) and RPMI broth were evaluated, following limited exposure to the MICs of the two polyenes, using an automated turbidometric method. For n...

Highly resolved emission and one-photon fluorescence excitation spectra for 1,4-diphenyl-1,3-butadiene seeded in a supersonic expansion of helium have been measured. The spectra show a long-lived (52.8 nsec for excitation at the 0-0) state at 29,652.5 cm(-1), approximately 1,150 cm(-1) below the well-characterized (1)B(u) state, which is assigned as (1)A(g)-i.e., we have directly observed a pol...

Viridenomycin is a structurally challenging, potentially biologically valuable molecule which has yet to succumb to total synthesis. Its instability, perhaps particularly associated with the northern polyene may contribute to the difficulties of piecing this molecule together. The synthesis of northern polyene models, including potentially stabilised analogues incorporating benzene rings as Z-a...

The isoprenoids, cholesterol and rubber, are known to arise from mevalonic (3,5-dihydroxy-3-methylvaleric) acid (5, 7). The same is true of carotenes (1, 6). Thus it has been found in this laboratory that mlevalonic acid is rapidly incorporated into carotenes and related compounds in the tonmato fruit (6). The hydrocarbon fraction of tomatoes previously incubated with 2-C'4-mevalonate contains ...

Selectivity in the catalytic functionalization of complex molecules is a major challenge in chemical synthesis. The problem is magnified when there are several possible stereochemical outcomes and when similar functional groups occur repeatedly within the same molecule. Selective polyene oxidation provides an archetypical example of this challenge. Historically, enzymatic catalysis has provided...

A survey of carotenoid—protein complexes is presented. Distinction is made between astaxanthin—proteins in which the absorption band of the carotenoid is unaltered in shape, and carotenoid—lipoglycoprotein complexes. The proposal by Buchwald and Jencks79 that the carotenoid is twisted about the double bonds of the polyene chain, is discussed and sustained for astaxanthin—proteins. A mode of bin...