Synthesis of Novel Enantiomerically Pure C ₃-Symmetric Trialkanolamine Ligand­ Containing Phosphoryl Groups

Abstract

Catalytic activity of ten metal salts in the reaction of benz­hydrylamine and benzylamine with diethyl 2,3-epoxypropylphosphonate (1) was studied. Only in the presence of copper(I) iodide pure diethyl 3-benzhydrylamino- and 3-benzylamino-2-hydroxy­propylphosphonates were produced quantitatively. Although the reactions­ catalysed by calcium(II) triflate were the fastest, they led to the contamination of the major products with the respective bisphosphonates. Enantiomerically pure (S,S)-bis[2-(O,O-diethyl­phosphorylmethyl)ethanol]amine (10) was prepared in a Ca(OTf)₂-catalysed reaction of (S)-1 (ee 94%) with 0.4 equivalent benzyl­amine followed by hydrogenolysis. The bisphosphonate (S,S)-10 was transformed into enantiomerically pure (S,S,S)-tris[2-(O,O-diethylphosphorylmethyl)ethanol]amine (2), when reacted with (S)-1 (ee 94%) or into (R,S,S)-2, when (R)-1 (ee 94%) was used.

Key words

amino alcohols - epoxides - ligands - phosphonates - ring opening

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