SB-3CT is a 2-[(arylsulfonyl)methyl]thiirane that achieves potent inhibition, by a thiirane-opening mechanism, of the MMP2 and MMP9 zinc metalloproteases. The deprotonation mechanism for thiirane opening of SB-3CT and for the opening of its oxirane analogue, both relevant to the inhibition of MMP2, was investigated computationally using the acetate anion as the Brønsted base and in methanol and...

An efficient, regioselective gold-catalyzed 1,3-transposition reaction of ynones and diynones has been developed. It was found that stereoelectronic (interrupted conjugation) and electronic (extended conjugation) factors could efficiently govern the regioselectivity of this thermodynamically controlled transformation. The produced conjugated diynones were efficiently transformed into diverse al...

The synthesis of a model endocyclic allene related to the vernonia allenes is described. Fragmentation of a suitable decalin derivative gave the simplified germacrane scaffold. Computational analysis of this and related substrates provides insight into the stereoelectronic requirements of C-C fragmentation. The overall strategy to access these and other sesquiterpenes and the key steps in the p...

Chiral C3-symmetric trisoxazolines are highly efficient stereodirecting ligands in enantioselective Cu(II) Lewis acid catalysis which is based on the concept of a stereoelectronic hemilability of the divalent copper; in direct comparison with the analogous bisoxazoline systems they are more efficient in the enantioselective alpha-amination as well as the enantioselective Mannich reaction of pro...

Using molecular mechanics (MM2, MM3) and semiempirical molecular orbital methods (EHMO, AMI, PM3) the relative energies were estimated from models for the tetrahedral intermediates in N->0 and o~N acyl migration in diastereoisomers of 3-amino-1,2,3triphenylpropanol to check the necessity of invoking a stereoe!ectronic effect to explain their reactivities . The molecular mechanics results correc...

Recently we described the Common REactivity PAttern (COREPA) technique to screen data sets of diverse structures for their ability to serve as ligands for steroid hormone receptors [1]. The approach identi®es and quanti®es similar global and local stereoelectronic characteristics associated with active ligands through a comparison of energeticallyreasonable conformer distributions for selected ...

An efficient synthesis of the C4-epi-lomaiviticin B core is reported. The synthesis features a diastereoselective anionic formal furan Diels-Alder reaction and a stereoselective oxidative enolate dimerization. During the investigation, subtle yet critical stereoelectronic effects imparted by the C4-stereocenter were observed.

Rotational coordinates about the C(3)–O(4) bonds of 2,4-dioxaheptane (DOH) and 2,4,6-trioxaheptane (TOH) are compared at correlated levels of electronic structure theory for gauche and trans orientations of the O(2)–C(3) bonds. TOH has overlapping anomeric effects, while DOH does not. The overlapping stereoelectronic effect shows its largest impact on the length of the O(2)–C(3) bond, which is ...