Csp2-H functionalization of phenols: an effective access route to valuable materials via Csp2-C bond formation.

In the vast majority of top-selling pharmaceutical and industrial products, phenolic structural motifs are highly prevalent. Non-functionalized simple phenols serve as building blocks in the synthesis of value-added chemicals. It is worth mentioning that lignin, being the largest renewable biomass source of aromatic building blocks in nature, mainly consists of phenolic units, which enable the production of structurally diverse phenols. Given their remarkable applicability in the chemical value chain, many efforts have been devoted to increasing the molecular complexity of the phenolic scaffold. Among the key techniques, direct functionalization of Csp2-H is a powerful tool, enabling the construction of new Csp2-C bonds in an economical and atomic manner. Herein we present and summarize the large plethora of direct Csp2-H functionalization methods that enables scaffold diversification of simple, unprotected phenols, leading to the formation of new Csp2-C bonds. In this review article, we intend to summarize the contributions that appeared in the literature mainly in the last 5 years dealing with the functionalization of unprotected phenols, both catalytic and non-catalytic. Our goal is to highlight the key findings and the ongoing challenges in the stimulating and growing research dedicated to the development of new protocols for the valorization of phenols.

The Halogen-Bond Nature in Noble Gas-Dihalogen Complexes from Scattering Experiments and Ab Initio Calculations.

In order to clarify the nature of the halogen bond (XB), we considered the prototype noble gas-dihalogen molecule (Ng-X2) systems, focusing on the nature, range, and strength of the interaction. We exploited data gained from molecular beam scattering experiments with the measure of interference effects to obtain a suitable formulation of the interaction potential, with the support of high-level ab initio calculations, and charge displacement analysis. The essential interaction components involved in the Ng-X2 adducts were characterized, pointing at their critical balance in the definition of the XB. Particular emphasis is devoted to the energy stability of the orientational Ng-X2 isomers, the barrier for the X2 hindered rotation, and the influence of the X2 electronic state. The present integrated study returns reliable force fields for molecular dynamic simulations in Ng-X2 complexes that can be extended to systems with increasing complexity and whose properties depend on the selective formation of XB.