The new sterically demanding phosphine 2-(di-o-tolylphosphino)phenol was pr
epared and used to create a series of eaters with N-acylated amino acids. T
he phosphine-containing esters react within 30-60 min at room temperature w
ith [(mu-Cl)Rh(cyclooctene)(2)](2) to give products of oxidative addition o
f the ester carbonyl-oxygen bond to the Rh center. The N-acyl carbonyl oxyg
en is bound to the Rh in these initial adducts, but is displaced upon addit
ion of PMe3. Remarkably, both initial products and their PMe3 adducts are f
ormed as single five-coordinate diastereomers in essentially quantitative y
ields. (C) 1999 Elsevier Science S.A. All rights reserved.