syn-1,2-Amino alcohols via diastereoselective allylic C-H amination.

syn-1,2-Amino alcohols are prevalent motifs in a diverse range of important small molecules such as natural products, pharmaceuticals, and asymmetric catalysts. The majority of methods for selectively constructing 1,2-amino alcohols rely on functional group interconversions or C-C bond-forming reactions using preoxidized materials.1 Selective methods for directly installing nitrogen functionality into inert C-H bonds have the potential to streamline the synthesis of these important compounds by avoiding the functional group manipulations (FGMs) required for working with oxidized materials.2,3 Herein we present a novel route for accessing chiral syn-1,2-amino alcohols enabled by the discovery of a Pd(II)/sulfoxide-catalyzed, diastereoselective allylic C-H amination reaction of chiral homoallylic N-tosyl carbamates (eq 1). To the best of our knowledge, this represents the first example of a general and stereoselective, catalytic allylic C-H amination reaction.4 We demonstrate that this reaction enables the streamlined synthesis of a diverse collection of syn-1,2-amino alcohols because of its broad scope and the versatility of its vinyl anti-oxazolidinone products.