An Electrophilic Cleavage Procedure for the Asymmetric Dihydroxylation: Direct Enantioselective Synthesis of Cyclic Boronic Esters from Olefins

A variation within the osmium‐catalysed asymmetric dihydroxylation (AD) of olefins is described that yields cyclic boronic esters from olefins in a straight‐forward manner. This process represents the first real product alteration in asymmetric dihydroxylation, since all previous protocols lead to f...

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Bibliographic Details
Published in:Chemistry : a European journal 2005-06, Vol.11 (13), p.3951-3958
Main Authors: Hövelmann, Claas H., Muñiz, Kilian
Format: Article
Language:English
Subjects:
alkenes
boronic esters
dihydroxylation
osmium
oxidation
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Summary:A variation within the osmium‐catalysed asymmetric dihydroxylation (AD) of olefins is described that yields cyclic boronic esters from olefins in a straight‐forward manner. This process represents the first real product alteration in asymmetric dihydroxylation, since all previous protocols lead to free diols exclusively. A protocol based on the Sharpless AD conditions (for enantioselective oxidation of prochiral olefins) was developed that gives cyclic boronic esters with excellent enantiomeric excesses (ee's). Some of the ee's are higher than those reported for conventional AD. The unprecedented role of phenyl boronic acid on the course of the AD reaction was investigated in detail. PhB(OH)2 does not interfere with the chiral ligand, leaving the enantioselective step of olefin oxidation intact. The main role of the boronic acids—apart from protecting the diol products against potential overoxidation—relies on removing the diol entity in an electrophilic cleavage, which is in contrast to the conventional hydrolytic cleavage of the AD protocols. Thus, a mechanistically new cleavage for enantioselective dihydroxylation reactions is introduced within the present work. A new cleavage concept for the Sharpless asymmetric dihydroxylation: Upon addition of aryl boronic acids to the reaction mixture, intermediately formed osmaglycolates are cleaved within an electrophilic attack of the boron reagent. Transesterification from osmium to boron ultimately leads to formation of stable cyclic boronic esters. The process is general for a wide range of alkenes leading to highly enantiomerically enriched boronic esters (see scheme).
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.200500095