Abstract
This account chronicles the iterative development of an enantioselective conjugate addition of organoboron nucleophiles to alpha,beta-unsaturated enones and enals catalyzed by BINOL derivatives. Beginning with a specific application of this transformation to the total synthesis of the flinderole alkaloids, the transformation progressed to encompass a much larger scope of heterocycle-substituted electrophiles. The next phase saw progress toward the use of a broader scope of functional nucleophiles, with application in a strategy to synthesize dis-coipyrrole D. At each stage of this chronologically organized discussion, key problems, hypotheses, and solutions are presented to show the sources of discovery and solutions to problems as the catalyst and other reaction components were made more reactive. The interplay of target-directed reaction development, efforts to increase the scope of compatible functional groups, mechanistic studies, and empirical exploration is described to illustrate sources of chemical discovery.