Electrooxidative Activation of B−B Bond in B₂cat₂: Access to gem‐Diborylalkanes via Paired Electrolysis

Abstract

This report describes the unprecedented electrooxidation of a solvent (e.g., DMF)-ligated B 2 cat 2 complex, whereby a solvent-stabilized boryl radical is formed via quasi-homolytic cleavage of the BÀ B bond in a DMF-ligated B 2 cat 2 radical cation. Cyclic voltammetry and density functional theory provide evidence to support this novel BÀ B bond activation strategy. Furthermore, a strategy for the electrochemical gemdiborylation of gem-bromides via paired electrolysis is developed for the first time, affording a range of versatile gem-diborylalkanes, which are widely used in synthetic society. Notably, this reaction approach is scalable, transition-metal-free, and requires no external activator.

Alkyl Triflimidate-Mediated Electrochemical Deaminative Functionalization

“…Furthermore, under catalytic base conditions and heating at 60°C, the deaminative oxidation of alkyl tri imidate 1 successfully yielded the corresponding ethers (49). Reaction of alkyl tri imidates with amides led to the formation of ester compounds (50)(51)(52)(53). Notably, alkyl tri imidates facilitated deamination Ritter reactions, e ciently producing a diverse array of amide compounds, including alkyl and aryl amides (54-61).…”

“…5H. [51][52][53][54][55] The reaction is initiated with rapid iodination of alkyl tri imidate to generate alkyl iodide.…”

Electrochemical synthesis and transformation of organoboron compounds

“…Very recently, the same group reported an electrochemical gem -diborylation of gem -bromides with B 2 cat 2 via paired electrolysis to give a range of versatile gem -diborylalkanes (Scheme 4b). 13…”

Regioselective 1,n-Diborylation of Alkylidenecyclopropanes Enabled by Catalysis with a Spirocyclic NHC IrIII Pincer Complex

“…In the past few years, particular attention has been devoted to the synthesis of gem -diborylalkanes and various strategies have been developed in the literature (Scheme c). Traditionally, gem -bis­(boryl)­alkanes are prepared through the reaction of bis­(boryl)­methyl metals with electrophiles, or the reaction of gem -dihaloalkanes with B 2 pin 2 . However, the use of strong bases and poor functional group tolerance limit the application of these methods.…”