A Generalized Picture of C–C Cross-Coupling

Transition metal
catalyzed cross-coupling reactions occupy a privileged
position in chemistry because of their ability to link myriad functional
groups. The numerous variants of this class of reactions (e.g., Suzuki,
Kumada, Negishi, etc.) differ in the transmetalation agent used to
transfer “R” groups onto the catalyst. While understanding
any single variant (e.g., Suzuki coupling) can be accomplished through
direct analysis of the catalytic cycle, a comprehensive picture that
illustrates the interrelationships between the different types of
cross-coupling reactions remains absent. Here, using a tool built
upon a three-dimensional volcano plot, we create a generalized thermodynamic
picture of C–C cross-coupling reactions. This “cross-coupling”
genome not only facilitates better understanding of catalytic behavior
but also outlines strategies for developing new reaction protocols
through the manipulation of easily computed descriptor variables.