- A comparative study of the relative stability of representative chiral and achiral boronic esters employing transesterification
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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.
- Roy, Chandra D.,Brown, Herbert C.
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- (R,R)-2,3-butanediol as chiral directing group in the synthesis of (αS)-α-chloro boronic esters
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(R,R)-2,3-Butanediol dichloromethane-boronate is a convenient reagent for attaching a chiral carbon to a Grignard or lithium reagent via zinc chloride catalyzed rearrangment of the intermediate borate complex, which yields (αS)-α-chloro boronic esters with 91-96% diastereoselectivity. The esters are easily hydrolyzed to crystalline boronic acids.
- Sadhu, Kizhakethil Mathew,Matteson, Donald S.,Hurst, Gerald D.,Kurosky, John M.
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p. 804 - 806
(2008/10/08)
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