Amino-Acid-Derived Amides as Stereodirecting Leaving Groups for Ferrier Rearrangement via Pd(0)-Catalyzed Tsuji–Trost Reactions

Abstract

Ferrier rearrangement on glycals is an efficient tool to form 2,3-dideoxy glycosides that provide access to various sugar derivatives through olefin functionalization. The classical acid-mediated transformation delivers the α-O-glycosides selectively. In this protocol, amides obtained from amino acids, glycine and proline, have been utilized as sustainable β-directing leaving groups on glycal substrates. The directing groups facilitate β-selective Ferrier rearrangements for hard alcohol nucleophiles by following the Pd(0)-catalyzed Tsuji–Trost inner sphere pathway.