Oxaziridine-Mediated Amination of Branched Allylic Sulfides:  Stereospecific Formation of Allylic Amine Derivatives via [2,3]-Sigmatropic Rearrangement

Abstract

Reaction of branched allylic sulfides with the N-Boc-oxaziridine 1 results in [2,3]-sigmatropic rearrangement of the intermediate allylic N-Boc-sulfimides with a high level of chirality transfer. The first example of formation of a quaternary stereocenter using this transformation is reported.

Advances in the Chemistry of Oxaziridines

“…When applied to chiral allylic sulfides, the reactions proceed with complete transfer of chirality. 110 Desulfurization of these compounds with triethyl phosphite results in ( E )-vinylglycine derivatives. Due to the mildness of the reaction conditions, a one-pot amination/rearrangement/N–S bond cleavage sequence can be performed in good overall yield (eq 27).…”

Simple Molecules, Highly Efficient Amination

“…By this method, allyl amine derivatives are prepared from allylic sulfi des through the rapid [2,3] -sigmatropic rearrangement of the resulting sulfi mides (Scheme 1.38 ). A high level of chirality transfer is observed in this rearrangement and a quaternary stereocenter is successfully constructed [45] .…”

Exploiting Organocatalysis: Enantioselective Synthesis of Vinyl Glycines by Allylic Sulfimide [2,3] Sigmatropic Rearrangement

“…In a continuation of our studies on transition‐metal‐free reagents for heteroatom transfer, we have developed the novel oxaziridine 2 , which acts as an efficient source of electrophilic nitrogen bearing a synthetically useful protecting group (Boc) 5. Recently, we used this reagent to extend the scope of the amination/[2,3] sigmatropic rearrangement of allylic sulfides,6 and showed for the first time (two examples) that this transformation can be effected efficiently on α,β‐unsaturated esters (Scheme ) 7. Essentially complete 1,3‐chirality transfer was observed in the rearrangement process.…”