A Unified Synthesis of Electron-Deficient 1,4- and 1,1,4-Substituted 1,3-Dienes through a Base-Promoted Allylation Followed by <i>Retro</i>-Michael Vinylogous Dehydrosulfinylation

We disclose a general 2-step synthesis of electron-poor 1,4- and 1,1,4-substituted buta-1,3-dienes bearing electron-withdrawing substituents at both termini of the conjugated system. The method relies on a base-promoted C-allylation of primary or secondary alkylsulfones with γ-bromocrotonate or related amide, nitrile, or sulfone and subsequent vinylogous <i>retro</i>-Michael dehydrosulfinylation. The geometry of the resulting dienes is substrate-dependent, and predominantly <i>E</i>,<i>E</i>-dienes are formed from <i>E</i>-electrophiles. This phosphorus- and transition-metal-free method tolerates a variety of functionalities and could serve as a supplement to Wittig, HWE, and Julia olefinations.