Pergamon Tetrahedron: Asymmetry 10 (1999) 1465–1470 Reaction of alcohols (via the Mitsunobu reaction) and alkyl halides with chiral selone derivatizing agents 1 Ruilian Wu, a,† Jerome D. Odom, b R. Bruce Dunlap b and Louis A. Silks III a,*,‡ a Los Alamos National Laboratory, Bioscience and Biotechnology Group, CST-4 MS, E-529, Los Alamos, NM 87545, USA b Department of Chemistry and Biochemistry, University of South Carolina, Columbia, SC 29208, USA Received 23 February 1999; accepted 30 March 1999 Abstract Coupling of a selone chiral derivatizing agent (CDA) to D, L-alkyl halides gives Se-alkylated adducts in yields ranging from 76–97%. Reaction of D, L-alcohols with the selone CDAs via the Mitsunobu reaction has given rise to Se-alkylated adducts in yields ranging from 82–92%. Examination of the 77 Se NMR spectra of the resulting diastereomeric adducts indicates that discrimination of remotely disposed chiral centers is possible using this technique. © 1999 Elsevier Science Ltd. All rights reserved. 1. Introduction The development of new chiral derivatizing agents (CDAs) for the determination of the chiral enrichment of chemical and enzymatic processes is an area that is being actively investigated. 2 We have developed chiral selone CDAs which allow for the determination of enantiomeric excesses (ees) of carboxylic acids, 3 acid chlorides, 4 alcohols, 5 amines 6 and amino acids 7 by 77 Se NMR spectroscopy. In addition, the use of these CDAs allows the assessment of the absolute configuration of the chiral center in some cases. 8 In an effort to increase the versatility of this method we have examined the reaction of alkyl halides and the direct coupling of alcohols via the Mitsunobu reaction to these selone CDAs. 9 Usually the ee determination of optically active organohalides is accomplished by measuring the optical rotation and comparing the value obtained to the literature value. This method gives rise to accurate determinations; however, it has some known drawbacks. 2 Development of a CDA capable of delivering the same information would be useful. * Corresponding author. Fax: 505-665-5052; e-mail: pete-silks@lanl.gov † Current address: CPBD, Inc., 300 Putnam Avenue, Cambridge, Massachusetts, 02139. Tel: (617)-868-2222 (ext. 246); e-mail: rwu@CPBD.com ‡ Adjunct Associate Professor, Department of Chemistry and Biochemistry, University of South Carolina, Columbia, South Carolina, 29208. 0957-4166/99/$ - see front matter © 1999 Elsevier Science Ltd. All rights reserved. PII: S0957-4166(99)00140-8 tetasy 2791 Article