Abstract
A number of N-(α-methylbenzyl) phosphorus amides were synthesized, and their stereochemical properties were studied. Reactions of achiral chlorophosphines with optically active α-methylbenzylamine are accompanied by asymmetric induction at the phosphorus atom to give optically active diastereoisomers of N-(α-methylbenzyl)aminophosphines, which were isolated as the corresponding borane complexes with 100% optical purity. Stereochemically pure (R,S)-aminophosphines were obtained by decomposition of these complexes via treatment with diethylamine. Their oxidation, sulfurization, and alkylation with methyl iodide afforded optically active aminophosphine derivatives. Hydrolysis of (R,S)-aminophosphines gave optically active tert-butylphenylphosphine oxide and phosphonic acid amides. (R,S)- and (S,S)-Diastereoisomers of N-(α-methylbenzyl)phosphinic amides were separated by crystallization and flash chromatography, and their absolute configuration was established. Also, derivatives of bis- and tris(α-methylbenzylamino)phosphines were synthesized.
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Kolodyazhnyi, O.I., Andrushko, N.V. & Grishkun, E.V. Stereoselective Reactions of Optically Active Derivatives of α-Methylbenzylaminophosphine. Russian Journal of General Chemistry 74, 515–522 (2004). https://doi.org/10.1023/B:RUGC.0000031849.78207.1c
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DOI: https://doi.org/10.1023/B:RUGC.0000031849.78207.1c