Comparing Neutral (Monometallic) and Anionic (Bimetallic) Aluminum Complexes in Hydroboration Catalysis: Influences of Lithium Cooperation and Ligand Set.

Bimetallic lithium aluminates and neutral aluminum counterparts are compared as catalysts in hydroboration reactions with aldehydes, ketones, imines and alkynes. Possessing Li-Al cooperativity, ate catalysts are found to be generally superior. Catalytic activity is also influenced by the ligand set, alkyl and/or amido. Devoid of an Al-H bond, iBu Al(TMP) operates as a masked hydride reducing benzophenone through a β-Η transfer process. This catalyst library therefore provides an entry point into the future design of Al catalysts targeting substrate specific transformations.