Catalytic asymmetric allylation of ketones and a tandem asymmetric allylation/diastereoselective epoxidation of cyclic enones.

A simple procedure is reported for the catalytic asymmetric allylation of ketones, utilizing titanium tetraisopropoxide, BINOL, 2-propanol additive, and tetraallylstannane as allylating agent. A variety of ketone substrates, including acetophenone derivatives and alpha,beta-unsaturated cyclic enones, reacted to form tertiary homoallylic alcohols in good yields (67-99%) and with high levels of enantioselectivity (generally >80%). A novel one-pot enantioselective allylation/diastereoselective epoxidation has also been introduced. Thus, upon completion of the allyl addition to conjugated cyclic enones, 1 equiv of tert-butyl hydroperoxide is added and the directed epoxidation of the allylic double bond ensues to afford the epoxy alcohol with high diastereoselectivity.

Atropisomeric amides: Achiral ligands with chiral conformations.

A new class of achiral ligands with atropisomeric conformations has been coordinated to titanium(IV). The ligands are ortho-hydroxy benzamide derivatives which are deprotonated on reaction with titanium tetraisopropoxide to furnish Ti(L)(2)(O-iPr)(2) complexes (L=ortho-phenoxy benzamide). In these octahedral titanium compounds, the ortho-phenoxy benzamide ligands chelate to titanium, bonding through the phenoxide oxygen and the amide carbonyl oxygen. The benzamide ligands adopt atropisomeric conformations with an angle between the aryl and amide groups of approximately 35 degrees. The ligand precursor, ligand, and titanium complexes have been characterized by X-ray crystallography. Only one diastereomer of each titanium complex was observed in the solid state structures.

Myxoid melanoma: immunohistochemical studies and a review of the literature.

Malignant myxoid melanoma (MMM) is a rarely reported variant of malignant melanoma, which can often be confused with other mucin-containing neoplasms. A retrospective study of 3 cases of MMM and a review of the English-language literature was performed. MMM affects an older population and is frequently misdiagnosed. The major pathologic features are atypical spindle cells embedded in a myxoid stroma. Immunohistochemistry analysis of the tumor shows uniform staining of the spindle cells with S-100. In our 3 cases, there were noticeably more mast cells that could be detected with Giemsa stain and with antibody against transforming growth factor. The prognosis appears to be equivalent to other primary melanomas. Diagnosing MMM requires a high index of suspicion. We hypothesize that mast cells and secretion of transforming growth factor beta stimulates fibroblast secretion of mucin, which contributes to the tumor's invasive potential.