We describe a systematic study of the scope and relationship between ligand structure and activity for a highly efficient and selective class of catalysts for the amination of heteroaryl and aryl chlorides, bromides and iodides containing sterically hindered chelating alkylphosphines. In the presence of this catalyst, aryl and heteroaryl chlorides, bromides and iodides react with many primary amines in high yields with part-per-million quantities of palladium precursor and ligand. Many reactions of primary amines with both heteroaryl and aryl chlorides, bromides and iodides occur to completion with 0.0005-0.05 mol % catalysts. A comparison of the reactivity of this catalyst for coupling of primary amines at these loadings is made with catalysts generated from hindered monophosphines and carbenes, and these data illustrate the benefits of chelation. Thus, these complexes constitute a fourth-generation catalyst for the amination of aryl halides, whose activity complements catalysts based on monophosphines and carbenes.

Mild palladium-catalyzed aminations of aryl tosylates and the first aminations of heteroaryl tosylates are described. In the presence of the combination of L2Pd(0) (L=P(o-tol)3) and the hindered Josiphos ligand CyPF-t-Bu, a variety of primary alkylamines and arylamines react with both aryl and heteroaryl tosylates at room temperature to form the corresponding secondary arylamines in high yields with complete selectivity for the monoarylamine. These reactions at room temperature occur in many cases with catalyst loadings of 0.1 mol % and 0.01 mol % in one case, constituting the most efficient aminations of aryl tosylates by nearly two orders of magnitude. This catalyst is make practical by the development of a convenient method to synthesize the L2Pd(0) precursor. This complex is stable to air as a solid. In contrast to conventional relative rates for reactions of aryl sulfonates, the reactions of aryl tosylates are faster than parallel reactions of aryl triflates, and the reactions of aryl tosylates are faster than parallel or competitive reactions of aryl chlorides.

Polyacrylamide gel analysis of the structural proteins of African and Asian strains of Chikungunya virus, an alphavirus, showed that both strains contain three structural proteins: glycosylated El and E2, embedded in the viral envelope, and a nonglycosylated nucleocapsid protein. In pulse-chase experiments the precursor protein PE2 was chased into glycoprotein E2, which migrated slightly faster than did glycoprotein El. The third Chikungunya glycoprotein, E3, was not associated with mature virions but was released into culture fluids. With glycoproteins El and E2, separated by glass wool column chromatography, it was shown that hemagglutinating activity is associated with glycoprotein El.

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Consecutive cyclization of allylaminoalkenes by tandem aminolithiation-carbolithiation proceeded smoothly by using a lithium amide as a lithiating agent as well as protonating agent to give bicyclic amines, octahydroindolizine and hexahydro-1 H-pyrrolizine, in reasonably high yield and diastereoselectivity.

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