{"database":"biostudies-literature","file_versions":[],"scores":null,"additional":{"submitter":["Iqbal SA"],"funding":["European Research Council","Higher Education Commission, Pakistan"],"pagination":["3865-3872"],"full_dataset_link":["https://www.ebi.ac.uk/biostudies/studies/S-EPMC10074396"],"repository":["biostudies-literature"],"omics_type":["Unknown"],"volume":["14(14)"],"pubmed_abstract":["Amide directed C-H borylation using ≥two equiv. of BBr<sub>3</sub> forms borenium cations containing a R<sub>2</sub>N(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."],"journal":["Chemical science"],"pubmed_title":["Amides as modifiable directing groups in electrophilic borylation."],"pmcid":["PMC10074396"],"funding_grant_id":["769599"],"pubmed_authors":["Iqbal SA","Nawaz I","Millet CRP","Ingleson MJ","Yuan K","Chotana GA","Nichol GS","Wang Z","Uzelac M","Jones TH"],"additional_accession":[]},"is_claimable":false,"name":"Amides as modifiable directing groups in electrophilic borylation.","description":"Amide directed C-H borylation using ≥two equiv. of BBr<sub>3</sub> forms borenium cations containing a R<sub>2</sub>N(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.","dates":{"release":"2023-01-01T00:00:00Z","publication":"2023 Apr","modification":"2025-04-19T04:37:15.236Z","creation":"2025-04-19T04:37:15.236Z"},"accession":"S-EPMC10074396","cross_references":{"pubmed":["37035693"],"doi":["10.1039/d2sc06483a"]}}