The Lithiation Reactivity and Selectivity of Differentially Branched Alkyldiphenylphosphine Oxides – A Simple and Versatile Approach to ortho‐Functionalized Arylphosphine Oxides

Alkyldiphenylphosphine oxides typically undergo α‐deprotonation with alkyllithium reagents. Here, the lithiation of differentially branched alkyldiphenylphosphine oxides was investigated and a diverse, but predictable reactivity was found. γ‐Branched derivatives undergo selective directed ortho‐metalation (DoM) using butyllithium and TMEDA as an additive. With decreasing degree of γ‐branching α‐lithiation becomes predominant. The ortho‐phosphinoyllithium intermediates are subject to functionalization and C C bond forming reactions, thus providing a convenient approach to new phosphine oxides and phosphine‐borane complexes, which have a good potential for an approach to new ligands for catalysis.