Chelation-assisted iridium-catalyzed hydroalkenylation and hydroarylation/cyclization with conjugated trienes.

Iridium-catalyzed hydroalkenylation of conjugated trienes by chelation-assisted alkenyl C-H activation of acrylamides has been demonstrated to produce 1,4,6-trienes atom efficiently with excellent - and / selectivities. In contrast, the reaction of benzamides and 1,3,5-trienes proceeds by a tandem hydroarylation of the trienes and cyclization intramolecular 1,2-addition, providing valuable -tetrahydroisoquinolinone derivatives. A broad range of aromatic and aliphatic 1,3,5-trienes bearing various functionalities were compatible to deliver target products with high yields and / selectivity.

Lignin-derived new hydrogen donors for photoinitiating systems in dental materials.

Objectives: The aim of this study is to develop amine free photo-initiating system (PIs) for the photopolymerization of dental methacrylate resins, using seven new hydrogen donors HDA-HDG derived from β-O-4 lignin model.

Methods: Seven experimental CQ/HD PIs were formulated with Bis-GMA/TEGDMA (70 w%/30 w%). CQ/EDB system was chosen as the comparison group.

Functionality-Directed Regio- and Enantio-Selective Olefinic C-H Functionalization of Aryl Alkenes.

Aryl alkenes represents one of the most widely occurring structural motif in countless drugs and natural products, and direct C-H functionalization of aryl alkenes provides atom- step efficient access toward valuable analogues. Among them, group-directed selective olefinic α- and β-C-H functionalization, bearing a directing group on the aromatic ring, has attracted remarkable attentions, including alkynylation, alkenylation, amino-carbonylation, cyanation, domino cyclization and so on. These transformations proceed by endo- and exo-C-H cyclometallation and provide aryl alkene derivatives in excellent site- stereo-selectivity.

Synthesis of 3-Oxo Quinolines by Cyclization Using Lignin Models and 2-Aminobenzyl Alcohols.

Phenoxy acetophenones were usually employed as β-O-4' lignin models for chemical conversion. Herein, an iridium-catalyzed dehydrogenative annulation between 2-aminobenzylalcohols and phenoxy acetophenones was demonstrated to prepare valuable 3-oxo quinoline derivatives, which are hard to prepare using previous methods. This operationally simple reaction tolerated a wide scope of substrates and enabled successful gram-scale preparation.

Ruthenium-catalyzed C-H amination of aroylsilanes.

Acylsilane represents a valuable synthon in synthetic chemistry. We report on ruthenium(ii)-catalyzed ortho-C-H amination of aroylsilanes to provide facile access to synthetically useful imidobenzoylsilanes and tosyl-amidobenzoylsilanes. The protocols, with broad substrate scope and excellent functional group tolerance, are enabled with the weak chelation-assistance of acylsilane via C-H cyclometallation.