La[N(SiMe₃)₂]₃-Catalyzed Ester Reductions with Pinacolborane: Scope and Mechanism of Ester Cleavage

Tris[N,N-bis(trimethylsilyl)amido]lanthanum (La^NTMS) is an efficient, highly active, and selective homogeneous catalyst for ester reduction with pinacolborane (HBpin). Alkyl and aryl esters are cleaved to the corresponding alkoxy- and aryloxy-boronic esters which can then be straightforwardly hydrolyzed to alcohols. Ester reduction is achieved with 1 mol % catalyst loading at 25-60 °C, and most substrates are quantitatively reduced in 1 h. Nitro, halide, and amino functional groups are well tolerated, and ester reduction is completely chemoselective over potentially competing intra- or intermolecular alkene or alkyne hydroboration. Kinetic studies, isotopic labeling, and density functional theory calculations with energetic span analysis argue that ester reduction proceeds through a rate-determining hydride-transfer step that is ligand-centered (hydride is transferred directly from bound HBpin to bound ester) and not through a metal hydride-based intermediate that is often observed in organolanthanide catalysis. The active catalyst is proposed to be a La-hemiacetal, [(Me₃Si)₂N]₂La-OCHR(OR)[HBpin], generated in situ from La^NTMS via hydroboronolysis of a single La-N(SiMe₃)₂ bond. These results add to the growing compendium of selective oxygenate transformations that La^NTMS is competent to catalyze, further underscoring the value and versatility of homoleptic lanthanide complexes in homogeneous catalytic organic synthesis.