Hypervalent iodine-mediated ß-difluoroalkylboron synthesis via an unusual 1,2-hydrogen shift enabled by boron substitution.

ß-Difluoroalkylborons, featuring functionally important CF2 moiety and synthetically valuable boron group, have great synthetic potential while remaining synthetically challenging. Herein we report a hypervalent iodine-mediated oxidative gem-difluorination strategy to realize the construction of gem-difluorinated alkylborons via an unusual 1,2-hydrogen migration event, in which the (N-methyliminodiacetyl) boronate (BMIDA) motif is responsible for the high regio- and chemoselectivity. The protocol provides facile access to a broad range of ß-difluoroalkylborons under rather mild conditions. The value of these products was demonstrated by further transformations of the boryl group into other valuable functional groups, providing a wide range of difluorine-containing molecules.

Diversity-Oriented Synthesis of α-Functionalized Acylborons and Borylated Heteroarenes by Nucleophilic Ring Opening of α-Chloroepoxyboronates.

The ring-opening reactions of N-methyliminodiacetyl (MIDA) α-chloroepoxyboronates with different nucleophiles allow the modular synthesis of a diverse array of organoboronates. These include seven types of α-functionalized acylboronates and seven types of borylated heteroarenes, some of which are difficult-to-access products using alternative methods. The common synthons, α-chloroepoxyboronates, could be viably synthesized by a two-step procedure from the corresponding alkenyl MIDA boronates. Mild reaction conditions, good functional-group tolerance, and generally good efficiency were observed. The utility of the products was also demonstrated.

Regio- and Diastereoselective Synthesis of Cyclohexadienylborons via an Intermolecular Diels-Alder Reaction of Alkenyl MIDA Boronates with 2-Pyrones.

An efficient synthesis of highly functionalized cyclohexadienylborons via an inverse electron-demand Diels-Alder reaction/CO2 extrusion of alkenyl MIDA boronates with 2-pyrones is outlined. By controlling the reaction temperature, the corresponding C(sp3 )-rich bicyclolactones could also be readily formed. The exo-selective reactions feature good functional-group tolerance, broad substrate scope, and excellent regio- and diastereoselectivity. Oxidation of the cyclohexadienylborons in a one-pot procedure led to the construction of aromatic boronates bearing valuable functional groups. Synthetic transformations of the C-B bond were demonstrated.

gem-Difluorination of Alkenyl N-methyliminodiacetyl Boronates: Synthesis of α- and ß-Difluorinated Alkylborons.

Organofluorine compounds are widely used in pharmaceutical, agrochemical, and materials sciences. The syntheses and applications of fluorinated organoborons facilitate the rapid and modular assemblies of fluorine-containing molecules because of the versatility of C-B bonds in diverse chemical transformations. Reported herein is a migratory geminal difluorination of aryl-substituted alkenyl N-methyliminodiacetyl (MIDA) boronates using commercially available Py⋅HF as the fluorine source and hyperiodine as the oxidant. The protocol offers facile access to α- and ß-difluorinated alkylboron compounds, both of which have previously been challenging to prepare. Mild reaction conditions, broad substrate scope, good functional-group tolerance, and moderate to good yields were observed. The utility of these products is demonstrated by further transformations of the C-B bond into other valuable functional groups.