Considerable effort for almost half a century has beendevoted to understanding how ligand steric and electronic properties modulatethe reactivity of a metal centre in a large number of catalytic processes. Thisis confounded by the fact that many of these transformations have two or moresteps in their catalytic cycles, which may mean that a favourable attribute inone step may act to disfavour another step. Many groups have worked diligentlyto develop methods to probe, and scales to grade ligand properties such thatthey can be used in, ideally, a predictive fashion to guide the development ofnew catalysts. In this presentation our approach to rational ligand design incross-coupling applications will be discussed and how this approach has beenused to improve catalyst performance. In particular, time will be dedicated tothe discussion of 1) the incorporation of secondary alkyl centres withoutisomerization and 2) in the introduction of primary amines without overarylation.

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