Binolam–AlCl: A Two‐Centre Catalyst for the Synthesis of Enantioenriched Cyanohydrin O ‐Phosphates

The enantioselective synthesis of cyanohydrin O ‐phosphates by using in situ generated bifunctional catalysts ( R )‐ or ( S )‐3,3′‐bis(diethylaminomethyl)‐1,1′‐binaphthol–aluminium chloride (binolam–AlCl) is reported. The reaction, which can be described as an overall cyano‐ O ‐phosphorylation of aldehydes, has a wide scope and applicability. Evidence is also provided, including ab initio and DFT calculations, in support of supported by the Lewis acid/Brønsted base (LABB) dual role of the catalyst in inducing first the key enantioselective hydrocyanation, which is then followed by O ‐phosphorylation. A brief screening of the synthetic usefulness of the resulting cyanohydrin O ‐phosphates unveiles some interesting applications. Among them, chemoselective hydrolysis, reduction and palladium‐catalysed nucleophilic allyl substitution, thereby leading to enantiomerically enriched α‐ O ‐phosphorylated α‐hydroxy esters, β‐amino alcohols and γ‐cyanoallyl alcohols, respectively. Naturally occurring (−)‐tembamide and (−)‐aegeline are synthesised accordingly.