604808-45-9Relevant academic research and scientific papers
Enantioselective synthesis of cyanohydrin O-phosphates mediated by the bifunctional catalyst binolam-AlCl
Baeza, Alejandro,Casas, Jesus,Najera, Carmen,Sansano, Jose M.,Saa, Jose M.
, p. 3143 - 3146 (2003)
(R)- and (S)-binolam-AICI complexes act as bifunctional catalysts to mediate the enantioselective cyanophosphorylation of aldehydes at room temperature. The resulting chiral cyanohydrin O-phosphates can be reduced to β-aminoalcohols or, when suitably substituted, can be transformed into γ-cyanoallylic alcohols through palladium-catalyzed allylic substitution, without loss of enantiomeric excess (see scheme).
Binolam-AlCl: A two-centre catalyst for the synthesis of enantioenriched cyanohydrin O-phosphates
Baeza, Alcjandro,Najera, Carmen,Sansano, Jose M.,Saa, Jose M.
, p. 3849 - 3862 (2007/10/03)
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/Bronsted 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.
