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How does the Achiral Base Decide the Stereochemical Outcome in the Dynamic Kinetic Resolution of Sulfinyl Chlorides? A Computational Study

  1. David Balcells1,2,
  2. Gregori Ujaque2,
  3. Inmaculada Fernández3,
  4. Noureddine Khiar4,
  5. Feliu Maseras1,2

Article first published online: 6 SEP 2007

DOI: 10.1002/adsc.200700096

Issue

Advanced Synthesis & Catalysis

Advanced Synthesis & Catalysis

Volume 349, Issue 13, pages 2103–2110, September 3, 2007

Additional Information

How to Cite

Balcells, D., Ujaque, G., Fernández, I., Khiar, N. and Maseras, F. (2007), How does the Achiral Base Decide the Stereochemical Outcome in the Dynamic Kinetic Resolution of Sulfinyl Chlorides? A Computational Study. Adv. Synth. Catal., 349: 2103–2110. doi: 10.1002/adsc.200700096

Author Information

  1. 1

    Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans 16, 43007 Tarragona, Catalonia, Spain, Fax: (+34)-977-920-231

  2. 2

    Unitat de Química Física, Universitat Autònoma de Barcelona, Edifici Cn, 08193 Bellaterra, Catalonia, Spain

  3. 3

    Departamento de Química Orgánica y Farmacéutica, Facultad de Farmacia, Universidad de Sevilla, c/Profesor García González 2, 41012 Sevilla, Spain

  4. 4

    Instituto de Investigaciones Químicas, C.S.I.C-Universidad de Sevilla, c/Américo Vespucio, Isla de la Cartuja, 41092 Sevilla, Spain

Publication History

  1. Issue published online: 18 SEP 2007
  2. Article first published online: 6 SEP 2007
  3. Manuscript Revised: 5 JUN 2007
  4. Manuscript Received: 12 FEB 2007

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Keywords:

  • asymmetric synthesis;
  • chirality;
  • diastereoselectivity;
  • dynamic kinetic resolution;
  • molecular modelling;
  • nucleophilic substitution

Abstract

The dynamic kinetic resolution of sulfinyl chlorides by addition of the optically active alcohol DAGOH (diacetone D-glucose) in the presence of non-chiral bases was theoretically studied at the ONIOM (Becke3LYP:UFF) level. The dependence of the stereochemical outcome on the nature of the base observed in this reaction was explored considering two electronically similar bases, pyridine and collidine, that are experimentally known to promote opposite diastereoselectivities. Our calculations reproduced the experimental result that the absolute configuration of sulfur in the major reaction product is R with pyridine but S with collidine. The analysis of the optimized geometries revealed that the most sterically active substituent around sulfur is the methyl of the substrate with pyridine but the base itself with collidine. This leads to an inversion of the chiral distribution of steric hindrance around sulfur that induces the reversal of the stereochemical outcome.

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