Varicella zoster virus encodes an immediate-early (IE) protein termed ORF61p that is orthologous to the herpes simplex virus IE protein ICP0. Although these proteins share several functional properties, ORF61p does not fully substitute for ICP0. The greatest region of similarity between these proteins is a RING finger domain. We demonstrate that disruption of the ORF61p RING finger domain by am...

The rearrangement of 1-alkynyl cyclobutanols and cyclopropanols to alkylidene cycloalkanones catalyzed by cationic triarylphosphine gold(I) complexes is described. The reaction tolerates terminal alkynes as well as alkyl, aryl, and halo-substitution at the acetylenic position and stereoselectively provides a single olefin isomer. The gold(I)-catalyzed rearrangement is stereospecific with regard...

Novel 5α-androstanes containing an isoxazoline moiety condensed to ring A or D were efficiently synthetized by 1,3-dipolar cycloadditions of aryl nitrile oxides to steroidal α,β-unsaturated ketones. During the ring closures, regioisomers in which the O terminus of the nitrile oxide dipoles is attached to the β-carbon of the dipolarophile were formed in a stereoselective manner to furnish exclus...

substitution product, Tp(PPh3)(CH3CN)RuCdC(Ph)CHCN (4). The cyclopropenyl ring in 3 and 4 is susceptible to ring opening by electrophiles such as CF3COOH, Ph3CPF6, and HgCl2. The substitution reaction of 3 with pyrazole is followed by an intramolecular nucleophilic addition of the nitrogen atom at the R-carbon atom to afford the metallacyclic complex, Tp(PPh3)Ru(C3H3NN)CdC(Ph)CH2CN (8a). The re...

Derivatives of etomidate were evaluated as inhibitors of adrenal steroid 11beta-hydroxylations. Stereoselective coupling by Mitsunobu produced chirally pure analogues to study the effect of configuration, modification of the ester, and substitution in the phenyl ring, with the aim to probe specific sites for introducing a radionuclide. Iodophenyl metomidate (IMTO) labeled with iodine-131 served...

The behaviour of various C(19) and C(18) steroids as substrates for crystalline preparations of cortisone reductase (EC 1.1.1.53) is described. 3alpha(Axial,3R)-, 3alpha(equatorial,3R)- and 3beta(axial,3S)-hydroxy steroid-NAD oxidoreductase activities are demonstrated. Four pairs of the substrates differed only in the shape of the a/b ring junction, three pairs differed only in substitution at ...

Bridgehead lithiations have successfully been carried out on substrates derived from catechinic acid, which possess the core bicyclo[3.3.1]nonane-1,3,5-trione structure present in garsubellin A. Using an external quench method, various electrophiles have been incorporated at the C-5 bridgehead position in a one-step process that appears to be sensitive to the substitution pattern on the bicycli...

In this study, ebselen and its analogues are shown to be catalysts for the decomposition of peroxynitrite (PN). This study suggests that the PN-scavenging ability of selenenyl amides can be enhanced by a suitable substitution at the phenyl ring in ebselen. Detailed mechanistic studies on the reactivity of ebselen and its analogues towards PN reveal that these compounds react directly with PN to...

The sign of the 1~ Cotton effects (CEs) at about 250-27D nm of the benzene chromophore of unsubstituted chiral phenylcarbinamines and their salts is determined by vibronic borrowing from the lBb-allowed transition at shorter wavelength. For these chiral phenylcarbinamines and their salts of the same generic absolute configuration, the sign of their lLb CEs is the same. On ring substitution, how...