“…Selective conversions of the vinylic sulfoximines II and allylic sulfoximines III to the enantio‐ and diastereopure building blocks IV − VIII can be envisaged considering (i) the facile lithiation of vinylic sulfoximines4,13−17 and allylic sulfoximines2,5,11,12,18−24 at C‐α, (ii) the ready nickel‐catalyzed cross‐coupling reaction of vinylic sulfoximines with organometallics,4,15,25,26 (iii) the excellent Michael acceptor properties of vinylic sulfoximines and their (dialkylamino)sulfoxonium salts,27−30 (iv) the facile reduction of sulfoximines,31 (v) the ready S N reaction of allylic sulfoximines with copper organyls,5−7 (vi) the facile elimination of β‐hydroxy (dialkylamino)sulfoxonium salts under formation of epoxides,32,33 and (vii) the ready substitution of allylic sulfoximines 34. Thus, if attainable, sulfoximines II and III would be expected to considerably expand the range of synthetic possibilities available through the use of either enantio‐ and diastereopure homoallylic alcohols of types II and III bearing an alkyloxy group,35−42 a Cl atom,43−45 a (dialkylamino)carbonyloxy group,10e,46−51 or a silyl group52−54 instead of the sulfonimidoyl group, or by utilizing aldol‐type compounds55,56 and vinylic epoxides as starting materials 57. The feasibility of a synthesis of II from I was indicated by the work of Reggelin et al,11,12 who showed that lithium−titanium exchange using ClTi(O i Pr) 3 of lithiated allyl and crotyl sulfoximines bearing a chiral N ‐(silyloxy)alkyl group instead of the N ‐methyl group allowed their γ‐hydroxyalkylation under the highly regio‐ and diastereoselective formation of vinylic hydroxy sulfoximines of type II in medium to good yields 58.…”