Regioselective C(sp ³ )–H borylation <i>via</i> a diarylboryl anion surrogate in sp ² –sp ³ diboranes(5)

Transition-metal-free C-H functionalization is a long-standing goal in synthetic chemistry. While a few main-group species have shown promise in C(sp²)-H activation through insertion or nucleophilic aromatic substitution (S_NAr) pathways, C(sp³)-H functionalization remains underdeveloped due to the intrinsic inertness of saturated carbon centers and the insufficient reactivity of reported main-group species. Herein, we report regioselective C(sp³)-H borylation in sp²-sp³ diboranes(5), mediated by a highly reactive B(<i>o</i>-tolyl)₂ ^- surrogate. It selectively inserts into α-C(sp³)-H bonds of alkyl groups to generate a family of anionic 1,1-diborylalkyl species. The resulting anions are readily converted to neutral <i>gem</i>-diborylalkanes by using TMSOTf. In substrates lacking α-C(sp³)-H bonds, β-C(sp³)-H activation becomes operative, producing organic salts and olefins. Competitive experiments reveal a clear preference for α- over β-C(sp³)-H activation. DFT calculations support a concerted insertion pathway and explain the preference for α- over β- and <i>ortho</i>-C-H activation. This study showcases the potential of reactive diarylboryl anion surrogates as powerful reagents for achieving regioselective C(sp³)-H borylation and expands the synthetic landscape of main-group-element-mediated C-H activation.