The direct and selective synthesis of phenols from aryl/heteroaryl halides and KOH has been achieved through the use of highly active monophosphine-based catalysts derived from Pd(2)dba(3) and ligands L1 or L2 and the biphasic solvent system 1,4-dioxane/H(2)O. We have also demonstrated a one-pot method of phenol formation/alkylation for the preparation of alkyl aryl ethers from aryl halides. In many instances, this protocol overcomes limitations in existing Pd-catalyzed coupling reactions of aliphatic alcohols with aryl halides. Finally, we demonstrate that substituted benzofurans can be prepared efficiently via a Pd-catalyzed phenol formation/cyclization protocol starting from 2-chloroaryl alkynes.

A good alternative: Highly reactive catalysts based on palladium and dialkylbiarylphosphino ligands provide unprecedented reactivity and selectivity in CN bond‐forming processes. The bulky monophosphine catalyst system Pd/1 was effective for the reaction of aryl/heteroaryl halides bearing primary amides and 2‐aminoheterocycles (see scheme; dba=dibenzylideneacetone, R=CONH2, NH2), thus showing that monodentate phosphines are viable alternatives to, and sometimes superior to, chelating ligands.

ACR20 response rates differed between secukinumab 75 mg, 150 mg and 300 mg doses and placebo; however, the primary efficacy endpoint was not achieved. Greater decreases in DAS28 were observed with secukinumab 75 mg, 150 mg and 300 mg than placebo. There were no unexpected safety signals and no specific organ-related toxicities. Further trials with secukinumab in the treatment of RA are warranted.

We present results on the amidation of aryl halides and sulfonates utilizing a monodentate biaryl phosphine-Pd catalyst. Our results are in accord with a previous report that suggests that the formation of kappa(2)-amidate complexes is deleterious to the effectiveness of a catalyst for this transformation and that their formation can be prevented by the use of appropriate bidentate ligands. We now provide data that suggest that the use of certain monodentate ligands can also prevent the formation of the kappa(2)-amidate complexes and thereby generate more stable catalysts for the amination of aryl chlorides. Furthermore, computational studies shed light on the importance of the key feature(s) of the biaryl phosphines (a methyl group ortho to the phosphorus center) that enable the coupling to occur. The use of ligands that possess a methyl group ortho to the phosphorus center allows a variety of aryl and heteroaryl chlorides with various amides to be coupled in high yield.

[reaction: see text] A selective and catalytic mono-N-alkylation method of both aromatic and aliphatic amines using nitriles as an alkylating agent with Pd/C or Rh/C as a catalyst is described. This method is particularly attractive to provide an environmentally benign and applicable alkylation method of amines without using toxic and corrosive alkylating agents such as alkyl halides and carbonyl compounds.