Secondary interaction in hydroxy-containing phosphinooxazolines

ORGN 31

Christina Moberg, kimo@kth.se and Anders Frölander. Department of Chemistry, KTH School of Chemical Science and Engineering, Stockholm, SE 100 44, Sweden
Phosphinooxazolines, first employed by Williams, Pfaltz, and Helmchen, serve as versatile ligands for a variety of asymmetric catalytic reactions. The hydroxy group in hydroxy-containing phosphinooxazolines such as 1 can take part in hydrogen bonding to low valent metal ions, thereby affecting the conformation and, as a result, the stereochemistry of catalytic reactions. The hydroxy group is also capable of coordinating to high valent metal ions via the oxygen atom, resulting in more rigid complexes. This leads for example to enhanced enantioselectivity in Rh- and Ir-catalyzed hydrosilylations of prochiral ketones. The influence of these secondary interaction on the conformation and dynamics of metal complexes and on the selectivity in catalytic reactions will be discussed.