There was stark contrast in the reactivity and the enantioselectivity of E1 and E2 in the HTS. Reactions with electrophile E1 generally gave low conversion and low ee. The reaction using L6 in MTBE provided the highest combination of conversion and selectivity (66% ee) with E1. Conversely, the HTS with electrophile E2 generally led to higher conversions and higher levels of ee. Reactions with ligands L2 and L6 resulted in high conversion in all solvents and moderate to high enantioselectivity in a selection of solvents. All reactions using ligand L4 resulted in insignificant conversion in any solvent, which is likely due to palladium coordination to a pyridyl nitrogen instead of a phosphine. Reactions with ligand L1 proved to be superior to the reactions with other ligands, as it exhibited impressive conversion and enantioselectivity in all solvents screened: MTBE (94% ee), THF (95% ee), DCE (98% ee), toluene (91% ee), and acetonitrile (98% ee). Overall, MTBE as solvent provides the highest conversion and enantioselectivity with both E1 and E2 electrophiles. A series of sterically and electronically differentiated electrophiles were evaluated using SIA 1 in the optimized conditions (Figure ). Despite the decrease in steric bulk, the reaction with methyl substituted allyl carbonate E3 exhibited high enantioselectivity and yield. Remarkably, unsubstituted allyl carbonate E4 reacts with high enantioselectivity (90:10 e.r.). The use of benzyl substituted allyl carbonate led to product 7, in high enantioselectivity and yield. The acrylate electrophiles yielding aza-Baylis-Hillman adducts 8 and 9 react in synthetically useful yields, albeit with low enantioselectivities. The p-methoxy phenyl substituted allyl carbonate was used leading to product 6 in high enantioselectivity and yield. Interestingly product 10, derived from the 1-napthyl allyl carbonate E9, was formed in high enantioselectivity (99:1 e.r.) and yield compared to its 2naphthyl substituted counterpart, 11 (69:31 e.r.). The effect of the naphthyl substitution on enantioselectivity suggests that enantioselectivity in the desymmetrization is not a simple result of increasing steric bulk of the 2-position of the allyl group. In general reactions with electrophiles with R 3 aryl and alkyl substitution results in products with the highest enantioselectivities.