The development of semi-stabilized, stabilized and functionalized ylides derived from short-chain trialkylphosphines in Wittig-type olefination reactions towards the synthesis alkenes, including stilbenes, styrenes and 1,3-dienes, as well as reagents for homologation reactions are described. The methods allow easy access to alkenes with high (E)-stereoselectivity in good yield. These reactions are conducted with weak bases in aqueous media and allow easy separation of water soluble phosphine oxides. The development of a mild organocatalytic process for the Wittig reaction and extension toward the preparation of reporter stilbenes under biological conditions is also described. Applications towards the preparation of biologically active natural products and derivatives are discussed.