A Scalable Biomimetic Synthesis of Resveratrol Dimers and Systematic Evaluation of their Antioxidant Activities

An efficient synthetic route to the resveratrol oligomers quadrangularin A and pallidol is reported. It features a scalable biomimetic oxidative dimerization that proceeds in excellent yield and with complete regioselectivity. A systematic evaluation of the natural products and their synthetic precursors as radical‐trapping antioxidants has revealed that, contrary to popular belief, this mode of action is unlikely to account for their observed biological activity.Hartnäckigkeit zahlt sich aus: Eine kurze Synthese der Resveratrol‐Oligomere Quadrangularin A und Pallidol macht sich die Stabilität der von 2,6‐Di‐tert‐butylphenol abgeleiteten Radikal‐ und der Chinonmethid‐Zwischenstufe zunutze. Untersuchungen dieser Verbindungen als antioxidative Radikalfänger ergaben, dass diese Eigenschaft höchstwahrscheinlich nicht die Ursache ihrer beobachteten biologischen Aktivität ist.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/110868/1/3825_ftp.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/110868/2/ange_201409773_sm_miscellaneous_information.pd

Inverting Conventional Chemoselectivity in Pd-Catalyzed Amine Arylations with Multiply Halogenated Pyridines

A new catalyst system capable of selective chloride functionalization in the Pd-catalyzed amination of 3,2- and 5,2- Br/Cl-pyridines is reported. A reaction optimization strategy employing ligand parametrization led to the identification of 1,1′-bis­[bis­(dimethyl­amino)­phosphino]­ferrocene “DMAPF”, a readily available yet previously unutilized diphosphine, as a uniquely effective ligand for this transformation