Ab Initio Structure/Reactivity Investigations of Illudin‐Based Antitumor Agents: A Model for Reaction in vivo

(Hydroxymethyl)acylfulvene (HMAF, irofulven; 4 ), a third‐generation derivative of a natural product extracted from the mushroom Omphalotus illudens, is selectively toxic towards certain forms of malignant tumors. Conversion of HMAF and cognates to stable aromatic derivatives is triggered by thiol attack in vitro and in vivo. Quantum‐chemical methods predict well the structure for several functionalized derivatives of irofulven as compared to known X‐ray crystallographic structures. Computational reaction profiles for thiol attack and aromatic rearrangement of irofulven and illudin S, a toxin from which irofulven is derived, provide insight into HMAF's selectivity and toxicity. Methods used include hybrid density‐functional theory (HDFT), Hartree? Fock (HF), and Møller? Plesset second‐order perturbation theory (MP2). Solvent effects have been explored by means of the new continuum‐solvation method, COSab, presented in an accompanying paper.     

The Hochschild class of the Chern character for semifinite spectral triples

We provide a proof of Connes’ formula for a representative of the Hochschild class of the Chern character for (p,∞)-summable spectral triples. Our proof is valid for all semifinite von Neumann algebras, and all integral p?1. We employ the minimum possible hypotheses on the spectral triples.     

Some refinements of Dade's projective conjecture

In this paper a further refinement of Dade's projective conjecture, due to Boltje, is presented. This new statement includes ideas first published by Isaacs and Navarro as well as the recent contractibility version of Alperin's conjecture introduced by Boltje. Leaning heavily on the work of Robinson, weaker forms of the conjecture are proved in the case of p-solvable groups.     

Molybdenum-catalyzed episulfidation of (E)-cycloalkenes with elemental sulfur

Episulfidation of (E)-cyclooctene and (E)-cyclononene was achieved with elemental sulfur by using a catalytic amount of a molybdenum oxo complex.