Anionic cross-coupling reaction of alpha-metallated alkenyl sulfoximines and alkenyl sulfoximines with cuprates featuring a 1,2-metal-ate rearrangement of sulfoximine-substituted higher order alkenyl cuprates and an alpha-metallation of alkenyl Sulfoximines by Cuprates

摘要

(E)- and (Z)-configured alpha-lithioalkenyl sulfoximines, which are available through lithiation of the corresponding alkenyl sulfoximines, undergo a anionic cross-coupling reaction (ACCR) with organocuprates with formation of the corresponding alkenyl cuprates and sulfinamide. The alkenyl cuprates can be trapped by electrophiles. The ACCR presumably proceeds via the formation of a higher-order sulfoximine-substituted alkenyl cuprate, which undergoes a 1,2-metalate rearrangement whereby the sulfoximine group acts as the nucleofuge. The parent (E)- and (Z)-configured alkenyl sulfoximines suffer upon treatment with an organocuprate a deprotonation at the alpha-position with formation of the corresponding alpha-cuprioalkenyl sulfoximines. These derivatives also enter into a similar ACCR with organocuprates. The ACCR of sulfoximines substituted homoallylic alcohols allows a stereoselective access to enantio- and diastereopure substituted homoallylic alcohols.