Highly Selective Allylborations of Aldehydes Using α, α‐Disubstituted Allylic Pinacol Boronic Esters1. (5th May 2014)

• Record Type: Journal Article
• Authors: Hesse, Matthew J.; Essafi, Stéphanie; Watson, Charlotte G.; Harvey, Jeremy N.; Hirst, David; Willis, Christine L.; Aggarwal, Varinder K.
• Is Part Of: Angewandte Chemie. Volume 126:Number 24(2014)
• Page Start: 6259
• Page End: 6263
• Publication Date: 2014-05-05
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201402995
• Languages: English
• ISSNs: 0044-8249

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>α, α‐Disubstituted allylic pinacol boronic esters undergo highly selective allylborations of aldehydes to give tetrasubstituted homoallylic alcohols with exceptional levels of <italic>anti</italic>‐<italic>Z</italic>‐selectivity (&gt;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.</p> </abstract>