Sulfonimidamides (SIAs) are aza-substituted variants of the sulfonamide functional group that were initially discovered in the 1950's. SIAs contain a stereogenic, configurationally stable, tetrahedral sulfur atom. The additional basic nitrogen adds a new vector in three-dimensional space that can act as both a hydrogen bond donor/acceptor while simultaneously providing a synthetic handle for further chemical transformations. Furthermore, N-acylated SIAs have been shown to be bioisosteres of carboxylic acids. As a result of these properties, the introduction of the SIA functional group into biologically active compounds has become an increasingly attractive target to medicinal chemists over the last two decades. More specifically, heterocyclic SIAs have started to emerge as an important structural motif in medicinally relevant molecules. This is exemplified by Novartis's NLRP3 compound and Hoffmann-La Roche's BACE1 inhibitors for Alzheimer's Disease 7 (Figure ). It was discovered that the stereochemistry at both the carbon and sulfur stereogenic centers significantly influenced the potency of the resulting BACE1 inhibitors. Despite the promising potential bioactivity of SIAs, synthetic reports of enantioenriched SIA heterocycles are rare. This notable absence in the literature is due to the fact that, until recently, methods to access SIAs containing enantiopure sulfur centers were limited. Classical methods were inefficient, involving separation via crystallization of diastereomers or the use of chiral auxiliaries. In the last few years, catalytic synthetic methods have developed to access enantioenriched SIAs (Figure ). One strategy for the synthesis of enantioenriched SIAs involves the generation of enantiopure sulfonimidoyl chlorides via chiral phosphoric acid catalysis followed by a stereospecific amination. Willis's strategy employs an enantioselective desymmetrization of SIAs. Symmetrically disubstituted SIAs tautomerize between their R/S enantiomers and the ions generated from deprotonation or protonation are prochiral. A bis-quaternized cinchona alkaloid was employed as a phase transfer catalyst that facilitated the reaction of a prochiral anion of the SIA with an alkyl halide electrophile yielding a variety of enantioenriched N-alkyl SIAs. Herein, we describe the development of a desymmetrization reaction of heterocyclic SIAs to provide facile access to these unexplored enantioenriched products. Sulfonamides are known to be competent nucleophiles in asymmetric alkylation reactions. We envisioned that SIAs, a closely related functional group to sulfonamides, should have similar reactivity in Tsuji-Trost asymmetric alkylation reaction. High throughput screening was employed for ligand and solvent optimization. The optimized reaction conditions lead to high enantioselectivities and yields for a variety of allylic electrophiles and SIA substrates. Additionally, we demonstrate how these compounds are amenable to further synthetic transformations and afforded access to novel enantioenriched tricyclic sulfonimidamides.