A Dichotomy in Cross-Coupling Site Selectivity in a Dihalogenated Heteroarene: Influence of Mononuclear Pd, Pd Clusters, and Pd Nanoparticles—the Case for Exploiting Pd Catalyst Speciation

Catalyst-Controlled Site-Selectivity Switching in Pd-Catalyzed Cross-Coupling of Dihaloarenes

Pd-catalyzed, site-selective mono-cross-coupling of substrates with two identical halo groups is a useful method for synthesizing substituted monohalogenated arenes. Such arenes constitute an important class of compounds, which are commonly identified as drug components and synthetic intermediates. Traditionally, these site-selective reactions have been realized in a “substrate-controlled” mann...

Connecting binuclear Pd(III) and mononuclear Pd(IV) chemistry by Pd-Pd bond cleavage.

Oxidation of binuclear Pd(II) complexes with PhICl(2) or PhI(OAc)(2) has previously been shown to afford binuclear Pd(III) complexes featuring a Pd-Pd bond. In contrast, oxidation of binuclear Pd(II) complexes with electrophilic trifluoromethylating ("CF(3)(+)") reagents has been reported to afford mononuclear Pd(IV) complexes. Herein, we report experimental and computational studies of the oxi...

Over-Expression of Immunosuppressive Molecules, PD-L1 and PD-L2, in Ulcerative Colitis Patients

Anionic Pd(0) and Pd(II) intermediates in palladium-catalyzed Heck and cross-coupling reactions.

The anions of PdCl(2)L(2) and Pd(OAc)(2), precursors of palladium(0) used in cross-coupling and Heck reactions, play a crucial role in these reactions. Tricoordinated anionic complexes Pd(0)L(2)Cl(-) and Pd(0)L(2)(OAc)(-) are the effective catalysts instead of the usually postulated Pd(0)L(2) complex. The anion ligated to the palladium(0) affects the kinetics of the oxidative addition to ArI as...

downregulation of immunosuppressive molecules, pd-1 and pd-l1 but not pd-l2, in the patients with multiple sclerosis

programmed cell death-1 (pd-1) and its ligands, pd-l1 and pd-l2, have been regarded as important immune system regulatory molecules. the aberrant expression of the molecules has been related to several autoimmune disorders. this study is aimed to assess the mrna expression level of pd-1, pd-l1, and pd-l2 molecules in the peripheral blood mononuclear mells (pbmcs) from multiple sclerosis (ms) pa...