Transition Metal Catalyst‐Free, Base‐Promoted 1,2‐Additions of Polyfluorophenylboronates to Aldehydes and Ketones

Abstract

An ovel protocol for the transition metal-free 1,2addition of polyfluoroaryl boronate esters to aldehydes and ketones is reported, which provides secondary alcohols,tertiary alcohols,a nd ketones.C ontrol experiments and DFT calculations indicate that both the ortho-F substituents on the polyfluorophenyl boronates and the counterion K + in the carbonate base are critical. The distinguishing features of this procedure include the employment of commercially available starting materials and the broad scope of the reaction with aw ide variety of carbonyl compounds giving moderate to excellent yields.I ntriguing structural features involving O À H•••O and O À H•••N hydrogen bonding,a sw ell as areneperfluoroarene interactions,inthis series of racemic polyfluoroaryl carbinols have also been addressed.

Visible-light-induced selective defluoroalkylations of polyfluoroarenes with alcohols

“…1b). Recently, Luo, Radius and Marder reported a transition metal-free, base-promoted additions of polyfluoroarylboronates to aldehydes and ketones, 43 based on their achievement on nickel-catalyzed defluoroborylation of polyfluoroarenes 44,45 and palladium-catalyzed dechloroborylation of chlorine-substituted polyfluoroarenes. 46 The usage of highly reactive or not easily accessible fluoroaryl reagents dramatically restricted the application of these methodologies and the variety of the products.…”

Silver(i) coordination polymers of trans-5-styrylpyrimidine – from structural diversity to solid-state reactivity under sunlight

“…Such a crystal represents a rare class of crystals for which Z ′ > 1. 21 Both the molecules are non-planar. The dihedral angles between the planes of the phenyl and pyrimidyl rings are respectively 24.5° and 26.5° for the two molecules.…”

Applications of Transition Metal-Catalyzed ortho-Fluorine-Directed C–H Functionalization of (Poly)fluoroarenes in Organic Synthesis

“…The significant exception is borylation, as the boronate esters or related derivatives are often isolable. However, it is important to note that electron-deficient fluorinated aryl boronates can be challenging substrates to employ due to rapid protodeboronation issues, and methodologies have been developed to utilize such organoboronates which circumvent this problem. ,− The generation of ortho -fluoro boronic acid derivatives remains a challenge. Industrially, the classical approach of lithiation and trapping with a borate ester remains the most prevalent method.…”