Chiral aldehydes in hydrocarbons: diastereoselective nucleophilic addition, NMR, and CD spectroscopy reveal dynamic solvation effects<FNR HREF="fn1"></FNR><FN ID="fn1">This article includes Supplementary Material available via the Internet at <URL XML-LINK="SIMPLE" HREF="http://www.interscience.wiley.com/jpages/0899-0042/suppmat/16/v16.50.html">http://www.interscience.wiley.com/jpages/0899-0042/suppmat/16/v16.50.html</URL>.</FN>

Temperature-dependent studies on the diastereoselective nucleophilic addition of n- BuLi to α-chiral aldehydes as (S)-O-(t-butyl-dimethylsilyl)lactal, (S)-O-(t-butyl-dimethylsilyl) mandelic aldehyde, and (R)-2-phenylpropanal in n-decane and n-dodecane reveal dynamic solvation phenomena with the presence of inversion temperatures (T<INF>inv</INF>) in the Eyring plots of ln (anti/syn) vs. 1/ T. These dynamic solvent effects were disclosed by temperature-dependent studies of the ¹³C NMR, CD, and UV spectra of the starting aldehydes in solution of n-decane and n-dodecane. The concomitant presence of three peculiar temperatures T<INF>CD</INF>, T<INF>UV</INF>, and T<INF>NMR</INF>, whose values are identical and match T<INF>inv</INF>, clearly confirms our earlier interpretation of the solvent-dependent nature of T<INF>inv</INF>. The inversion temperature, as well as T<INF>CD</INF>, T<INF>UV</INF>, and T<INF>NMR</INF> represents the interconversion temperature of two different solvation clusters which act as two different supramolecules with different stereoselectivities. Chirality 16:50–56, 2004. © 2003 Wiley-Liss, Inc.