Open AccessElectron‐rich O=PR 3 compounds: Catalysts for alcohol silylation
Author(s) -
Liu Xiaodong,
Verkade John G.
Publication year - 2001
Publication title -
heteroatom chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.283
H-Index - 42
eISSN - 1098-1071
pISSN - 1042-7163
DOI - 10.1002/1098-1071(2001)12:1<21::aid-hc5>3.0.co;2-a
Subject(s) - chemistry , moiety , silylation , heteroatom , catalysis , alcohol , chloride , medicinal chemistry , organic chemistry , phenols , ring (chemistry)
The catalytic effect of a group of R 3 P=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 R 3 P=O is an efficient catalyst in such reactions when R is a good electron‐donating group, such as Me 2 N or n‐Bu and as an NMe(CH 2 ) moiety in N(CH 2 CH 2 NMe) 3 P=O ( 3 ). However, R 3 P=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 CH 2 N‐o‐CH 2 C 5 H 4 N moiety in N(CH 2 CH 2 N‐o‐CH 2 C 5 H 4 N) 3 P=O. Compound 3 , synthesized by oxidation of commercially available N(CH 2 CH 2 NMe) 3 P, 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