Calculations with Gaussian orbitals and periodic boundary conditions using several density functionals are carried out to study the proton-doping of polyaniline. We explore previously proposed mechanisms to explain the spectacular increase of the electrical conductivity of polyaniline upon protonation. The structural and spectroscopic theoretical predictions for both polaron and bipolaron lattices agree quite well with the experimental data, and we find that the bipolaron structure is lower in energy.
In order to achieve reproducibility during iridium-photoredox and nickel dual-catalyzed sp(3)-sp(2) carbon-carbon bond-forming reactions, we investigated the role that molecular oxygen (O2), solvent and light-source (CF lamp or blue LED) play in a variety of Ir-photoredox mediated transformations. The presence of O2 was discovered to be important for catalyst activation when air-stable Ni(II) precatalysts were used in DMF under CF lamp irradiation; however, O2 was not required for catalysis when conducted with Ni(COD)2 in the same reaction system. O2 is believed to promote rapid reduction of the Ni(II) precatalyst by Ir(II) to Ni(0). In addition to O2, the effects that solvent and light-source have on the dual-catalyzed decarboxylative cross-coupling reactions will be discussed. These findings have enabled us to develop a more robust dual-catalyzed decarboxylative cross-coupling protocol.
Simple 1,3-dienes undergo highly stereoselective hetero-Diels-Alder additions with SO2 at low temperature giving sultines. These reactions that are faster than the more exothermic cheletropic additions of SO2-producing sulfolenes. This has led to the invention of a new C-C bond-forming reaction combining electron-rich dienes and alkenes with SO2. The reaction cascade has been exploited to develop combinatorial, one-pot, four-component syntheses of polyfunctional sulfones, sulfonamides, and sulfonic esters. It also allows us to generate, in one-pot operations, enantiomerically enriched polypropionate fragments containing up to three contiguous stereogenic centers and a (E)-alkene unit. These fragments can be used directly in further C-C bond-forming reactions, such as cross-aldol condensations, thus permitting the expeditious construction of complicated natural products of biological interest (e.g., Baconipyrones, Rifamycin S, Apoptolidinone) and analogues. New ene reactions of SO2 have also been discovered; they open new avenues to organic synthesis.
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