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A Comparative Study of the Relative Stability of Representative Chiral and Achiral Boronic Esters Employing Transesterification

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Summary.

A comparative study of the transesterification of five representative chiral and achiral boronic esters with various structurally modified diols was undertaken to qualitatively understand the factors influencing the relative stability of these boronic esters. Several factors such as chelation, conformation, steric bulk of the substituents, size of the heterocycle, and entropy influence the relative rate of transesterification as well as the stability of the boronic esters. Amongst these boronic esters, pinanediol phenylboronic ester was found to be the most stable boronic ester whereas DIPT boronic ester appeared to be thermodynamically the least stable one. The transesterification with sterically hindered diols was observed to be relatively slow, but afforded thermodynamically more stable boronic esters. Boronic esters derived from cis-cyclopentanediols and the bicyclo[2.2.1]heptane-exo,exo-2,3-diols are relatively more stable. This study not only presents the qualitative picture of relative stability of various boronic esters, but also provides helpful hints regarding the possible recovery of chiral auxiliaries. Many C 2-symmetric chiral auxiliaries, such as 2,3-butanediol, 2,4-pentanediol, DIPT, and cis-cyclohexane-1,2-diol, can be retrieved by simple transesterification of the corresponding boronic esters with commercial inexpensive diols, such as pinacol, 1,3-propanediol, and neopentyl glycol.

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Authors and Affiliations

  1. Herbert C. Brown Center for Borane Research, Department of Chemistry, Purdue University, West Lafayette, IN, USA

    Chandra D. Roy & Herbert C. Brown

  2. EMD Biosciences, Inc., San Diego, CA, USA

    Chandra D. Roy

Authors
  1. Chandra D. Roy
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  2. Herbert C. Brown
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Corresponding author

Correspondence to Chandra D. Roy.

Additional information

This paper is dedicated to the memory of my mentor, the late Professor Herbert C. Brown (1912–2004). Professor Herbert C. Brown deceased on December 19, 2004. The work described herein was carried out at Purdue University during my stay as a post-doctoral research associate

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Roy, C., Brown, H. A Comparative Study of the Relative Stability of Representative Chiral and Achiral Boronic Esters Employing Transesterification. Monatsh. Chem. 138, 879–887 (2007). https://doi.org/10.1007/s00706-007-0699-x

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  • DOI: https://doi.org/10.1007/s00706-007-0699-x

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