| Abstract: | The catalytic effect of a group of R3P=O compounds was studied in a mild procedure for the silylation of primary alcohols, secondary alcohols, hindered secondary alcohols, and of hindered phenols in the presence of t‐butyldimethylsilyl chloride (TBDMSCl) and t‐butyldiphenylsilyl chloride (TBDPSCl). It was found that R3P=O is an efficient catalyst in such reactions when R is a good electron‐donating group, such as Me2N or n‐Bu and as an NMe(CH2) moiety in N(CH2CH2NMe)3P=O ( 3 ). However, R3P=O is a weak or ineffective catalyst when R is a poor electron‐donating group, such as Ph or O‐n‐Bu or as a CH2N‐o‐CH2C5H4N moiety in N(CH2CH2N‐o‐CH2C5H4N)3P=O. Compound 3 , synthesized by oxidation of commercially available N(CH2CH2NMe)3P, displayed the best catalytic properties for alcohol silylation in terms of efficiency, stability, and safety. © 2001 John Wiley & Sons, Inc. Heteroatom Chem 12:21–26, 2001 |
