Understanding of the 1,4-addition of organocuprates, especially LiCuR₂ species, to enone Michael acceptors has blossomed in the light of recent kinetic, NMR, and theoretical investigations. These investigations have been reviewed and are compared to the various reaction co-ordinates they support. Emphasis is placed on relating the theoretical calculations to physical data extracted from real systems. The mechanism of cuprate conjugate addition is compared to related reactions including: additions to ynones, alkene carbocupration, and S_N2′ allylic and propargylic substitution reactions.

When the first titanium complex with anticancer activity was identified in the 1970s, it was attractive, based on the presence of the dichloride unit in TiCl₂Cp₂ (Cp = η-C₅H₅)₂, to assume its mode of biological action was closely aligned with cisplatin [cis-PtCl₂(NH₃)₂]. Over the intervening 40 years however a far more complicated picture has arisen indicating multiple cellular mechanisms of cellular action can be triggered by titanium anti-cancer agents. This tutorial review aims to unpick the historical data and provide new researchers, without an explicit cancer biology background, a contemporary interpretation of both older and newer literature and to review the best techniques for attaining the identities of the biologically active titanium species and how these interact with the cancer cellular machinery.