biostudies-literatureIqbal SAEuropean Research CouncilHigher Education Commission, Pakistan3865-3872https://www.ebi.ac.uk/biostudies/studies/S-EPMC10074396biostudies-literatureUnknown14(14)Amide directed C-H borylation using ≥two equiv. of BBr₃ forms borenium cations containing a R₂N(R')C[double bond, length as m-dash]O→B(Ar)Br unit which has significant Lewis acidity at the carbonyl carbon. This enables reduction of the amide unit to an amine using hydrosilanes. This approach can be applied sequentially in a one-pot electrophilic borylation-reduction process, which for phenyl-acetylamides generates <i>ortho</i> borylated compounds that can be directly oxidised to the 2-(2-aminoethyl)-phenol. Other substrates amenable to the C-H borylation-reduction sequence include mono and diamino-arenes and carbazoles. This represents a simple method to make borylated molecules that would be convoluted to access otherwise (<i>e.g. N</i>-octyl-1-BPin-carbazole). Substituent variation is tolerated at boron as well as in the amide unit, with diarylborenium cations also amenable to reduction. This enables a double C-H borylation-reduction-hydrolysis sequence to access B,N-polycyclic aromatic hydrocarbons (PAHs), including an example where both the boron and nitrogen centres contain functionalisable handles (N-H and B-OH). This method is therefore a useful addition to the metal-free borylation toolbox for accessing useful intermediates (ArylBPin) and novel B,N-PAHs.Chemical scienceAmides as modifiable directing groups in electrophilic borylation.PMC10074396769599Iqbal SANawaz IMillet CRPIngleson MJYuan KChotana GANichol GSWang ZUzelac MJones THfalseAmides as modifiable directing groups in electrophilic borylation.Amide directed C-H borylation using ≥two equiv. of BBr₃ forms borenium cations containing a R₂N(R')C[double bond, length as m-dash]O→B(Ar)Br unit which has significant Lewis acidity at the carbonyl carbon. This enables reduction of the amide unit to an amine using hydrosilanes. This approach can be applied sequentially in a one-pot electrophilic borylation-reduction process, which for phenyl-acetylamides generates <i>ortho</i> borylated compounds that can be directly oxidised to the 2-(2-aminoethyl)-phenol. Other substrates amenable to the C-H borylation-reduction sequence include mono and diamino-arenes and carbazoles. This represents a simple method to make borylated molecules that would be convoluted to access otherwise (<i>e.g. N</i>-octyl-1-BPin-carbazole). Substituent variation is tolerated at boron as well as in the amide unit, with diarylborenium cations also amenable to reduction. This enables a double C-H borylation-reduction-hydrolysis sequence to access B,N-polycyclic aromatic hydrocarbons (PAHs), including an example where both the boron and nitrogen centres contain functionalisable handles (N-H and B-OH). This method is therefore a useful addition to the metal-free borylation toolbox for accessing useful intermediates (ArylBPin) and novel B,N-PAHs.2023-01-01T00:00:00Z2023 Apr2025-04-19T04:37:15.236Z2025-04-19T04:37:15.236ZS-EPMC100743963703569310.1039/d2sc06483a