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Highly Selective Allylborations of Aldehydes Using α,α‐Disubstituted Allylic Pinacol Boronic Esters
Author(s) -
Hesse Matthew J.,
Essafi Stéphanie,
Watson Charlotte G.,
Harvey Jeremy N.,
Hirst David,
Willis Christine L.,
Aggarwal Varinder K.
Publication year - 2014
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201402995
Subject(s) - pinacol , allylic rearrangement , chemistry , stereoselectivity , selectivity , boronic acid , borylation , organic chemistry , combinatorial chemistry , catalysis , aryl , alkyl
α,α‐Disubstituted allylic pinacol boronic esters undergo highly selective allylborations of aldehydes to give tetrasubstituted homoallylic alcohols with exceptional levels of anti ‐ Z ‐selectivity (>20:1). The scope of the reaction includes both acyclic and cyclic allylic boronic esters which lead to acyclic and exocyclic tetrasubstituted homoallylic alcohols. The use of β‐borylated allylic boronic esters gave fully substituted alkenes bearing a boronic ester which underwent further cross‐coupling enabling a highly modular and stereoselective approach to the synthesis of diaryl tetrasubstituted alkenes. Computational analysis revealed the origin of the remarkable selectivity observed.