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We have proposed the convenient synthesis of new aminomethylphosphinic acids and their derivatives containing N-alkyl 4-hydroxypiperidines moieties. So the addition of bis(trimethylsiloxy)phosphine to N-alkyl 4-piperidones proceeds under mild conditions to give PH-phosphinates as key compounds for preparation of trimethylsilyl esters of above acids via interaction with various aminals. The further treatment of trimethylsilyl esters with the methanol resulted in the corresponding acids.