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Developed initially in the 1990s to meet the needs of high-throughput screening, combinatorial chemistry delivered large libraries of compounds which did not meet the initial hype of the practitioners. However, 20 years of research understanding the issues, and the parallel development of a large commercial market for compound supply now allows collections to meet the needs of the early stages of drug discovery. This chapter will highlight the key discoveries (and mistakes) along that path, and discuss the selection processes now in widespread use to build highly efficient and cost-effective screening libraries.

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