A practical guide for the assignment of the absolute configuration of alcohols, amines and carboxylic acids by NMR is presented, The guide includes information required for the judicious selection of the most suitable auxiliary reagent (MPA, MTP, BPG, 9-AMA and 9-AHA), derivatization procedures and NMR conditions (solvent and temperature) for each substrate, as well as a critical account on the reliability, scope and limitations of these applications. (C) 2002 Elsevier Science Ltd. All rights reserved.