New oxidative dehydrogenative couplings of pyrazol-5-amines for the selective synthesis of azopyrrole derivatives have been described. The former reaction simultaneously installs C-I and N-N bonds through iodination and oxidation, whereas the latter involved a copper-catalyzed oxidative coupling process. The resulting iodo-substituted azopyrroles were employed by treatment with various terminal...

Catalytic enantiotopic-group-selective cross-couplings of achiral geminal bis(pinacolboronates) provide a route for the construction of nonracemic chiral organoboronates. In the presence of a chiral monodentate taddol-derived phosphoramidite ligand, these reactions occur with high levels of asymmetric induction. Mechanistic experiments with chiral (10)B-enriched geminal bis(boronates) suggest t...

Considerable efforts have been undertaken by numerous groups in academia and industry over the past decade to expand the repertoire of coupling reagents in palladium(0)-catalyzed cross-coupling reactions. In particular, alkenyl phosphates and tosylates have proven their worth in various cross-coupling reactions, such as the Stille, Suzuki, 3] Negishi, Kumada, Sonogashira, b,e,f,5] Buchwald–Hart...

We herein showcase the ability of NHC-coordinated dinuclear NiI -NiI complexes to override fundamental reactivity limits of mononuclear (NHC)Ni0 catalysts in cross-couplings. This is demonstrated with the development of a chemoselective trifluoromethylselenolation of aryl iodides catalyzed by a NiI dimer. A novel SeCF3 -bridged NiI dimer was isolated and shown to selectively react with Ar-I bon...

We present a safe and convenient cross-coupling strategy for the large-scale synthesis of biaryls, commercially important structures often found in biologically active molecules. In contrast to traditional cross-couplings, which require the prior preparation of organometallic reagents, we use a copper catalyst to generate the carbon nucleophiles in situ, via decarboxylation of easily accessible...

We have carried out an ab initio electronic structure calculations of electron transfer couplings between chromophores in the bacterial photosynthetic reaction center. The couplings agree remarkably well with parameters obtained from recent quantum dynamical modeling of experimental data assuming an explicit intermediate mechanism. We also have computed couplings on the M-side of the reaction c...

We calculate the cross section of Higgs boson production in the reaction e + e − → ν ¯ νb ¯ b for the case of left and right longitudinally polarized electron beam. Complete set of signal and irreducible background diagrams is considered. We propose a new critical test to identify the Higgs boson provided by the ratio of cross sections with left and right beam polarization. This quantity is sen...

Building on the known photophysical properties of well-defined copper-carbazolide complexes, we have recently described photoinduced, copper-catalyzed N-arylations and N-alkylations of carbazoles. Until now, there have been no examples of the use of other families of heteroatom nucleophiles in such photoinduced processes. Herein, we report a versatile photoinduced, copper-catalyzed method for c...

We describe a time-dependent wavepacket based method for the calculation of the state-to-state cross sections for the Cl+H(2) reaction including all couplings arising from the nonzero spin and electronic orbital angular momenta of the Cl atom. Reactant-product decoupling allows us to use a physically correct basis in both the reactant and the product arrangements. Our calculated results agree w...

The cross section for U+ production from the reaction gp→p+K−U+, which was observed in the CLAS experiment at the Jefferson National Laboratory, is evaluated in a hadronic model that includes couplings of U+ to both KN and K*N. With their coupling constants determined from the empirical pNNs1710d and rNNs1710d coupling constants using the SU(3) symmetry, the cross section for this reaction has ...