The addition of silylphosphines to chiral aldehydes proceeds with high diastereoselectivity to give optically pure tertiary α-trimethylsiloxyalkylphosphines. The diastereomeric excesses of the addition products were achieved to 90-100%. The reaction of bis(trimethylsilyl)phenylphosphine with the acetonide of (R)-glyceraldehyde provides diastereomerically enriched tertiary bis(glyceryl)phosphines.
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