Industrial reaction improved: The first monocarbenepalladium(0)–olefin complex has been isolated and characterized (see structure; Pd orange, N green, S yellow, O blue). The complex exhibited unprecedented high catalyst productivity and selectivity for industrially important telomerization reactions (the dimerization of 1,3‐dienes in the presence of a nucleophile, in this case an alcohol).

[reaction: see text] The Heck reaction of aryl chlorides was investigated in the presence of defined monocarbenepalladium(0) complexes. Activated and nonactivated aryl chlorides provide the corresponding cinnamic esters and stilbenes in (n)Bu(4)NBr as a ionic liquid in good to excellent yields.

New Pd(0) olefin complexes, 2−5, of a binaphthalene-based chiral P,N(oxazoline) auxiliary, (S,R)-2-[4-(isopropyl)oxazol-2-yl]-2‘-diphenylphosphino-1,1‘-binaphthyl, 1, have been prepared (olefin = fumaronitrile, maleic anhydride, 4-cyclopentene-1,3-dione, and dibenzylideneacetone). These compounds reveal different dynamic behavior in solution as shown by 2-D exchange spectroscopy. Ligand 1 affords excellent enantioselectivity (up to 99% ee) in the allylic amination of a 1,3-diphenyl allyl precursor. The solid-state structure of [Pd(η3-PhCHCHCHMe)(1)]OTf, 15, has been determined and shows two different diastereomeric cations within one unit cell; that is both the si and re faces of the allyl crystallize together, the first example of this for a moderately large allyl ligand. The structure of PdCl2(1) is also reported and reveals (as does that for 15) that the oxazoline ring of 1 is twisted relative to the P−Pd−N coordination plane, thus placing this ring substituent above and not below the coordination plane. A more exact solid-state structure for Pd2(dba)3 has been determined.

The first monocarbenepalladium(0) complexes with benzoquinone and naphthoquinone as additional ligands have been prepared. As demonstrated by NMR spectroscopy and X‐ray analysis, the complexes show a unique coordination mode giving quinone‐bridged dimers. The monocarbenepalladium(0) complexes allow efficient cross‐coupling reactions of aryldiazonium salts with olefins (Heck reaction) and arylboronic acids (Suzuki reaction).

RORγt is an important nuclear receptor that regulates the production of several pro-inflammatory cytokines such as IL-17 and IL-22. As a result, RORγt has been identified as a potential target for the treatment of various immunological disorders such as psoriasis, psoriatic arthritis, and inflammatory bowel diseases. Structure and computer-assisted drug design led to the identification of a novel series of tricyclic RORγt inverse agonists with significantly improved in vitro activity in the reporter (Gal4) and human whole blood assays compared to our previous chemotype. Through careful structure activity relationship, several potent and selective RORγt inverse agonists have been identified. Pharmacokinetic studies allowed the identification of the lead molecule 32 with a low peak-to-trough ratio. This molecule showed excellent activity in an IL-2/IL-23-induced mouse pharmacodynamic study and demonstrated biologic-like efficacy in an IL-23-induced preclinical model of psoriasis.