Nc. Demello et Dp. Curran, STEREOSELECTION AT THE STEADY-STATE BY STEREOCONVERGENT REACTION TOPOGRAPHY, Journal of the American Chemical Society, 120(2), 1998, pp. 329-341
A novel strategy for achieving stereoselection by engineering reaction
s to occur through a unique kinetic scheme is introduced. The strategy
, named ''complex stereoselection'', effects stereoselection as a resu
lt of intermediates at the steady state partitioning successively betw
een competing chemical transformations. A mathematical description of
the ratio of products produced in the kinetic strategy is derived, and
computer simulation of that model demonstrates two principal advantag
es of this method: higher selectivity and more efficient conversion of
substrates. These computer simulations were subsequently used to dete
rmine conditions for maximum stereoselection in these reactions via th
e framework of a series of hypothetical scenarios in six different inc
arnations of complex stereoselection. The resulting predictions presen
t challenges to the field of experimental stereochemistry.