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We have developed and applied an approach to reaction discovery that takes advantage of DNA encoding, DNA-programmed assembly of substrate pairs, in vitro selection, and PCR amplification, yet does not require reaction conditions that support DNA hybridization. This system allows the simultaneous evaluation of &gt;200 potential bond-forming combinations of substrates in a single experiment and can be applied in a range of solvent and temperature conditions. In an initial application, we applied this system to explore Au(III)-mediated chemistry and uncovered a simple, mild method for the selective Markovnikov-type hydroarylation of vinyl arenes and trisubstituted olefins with indoles.

Development and Initial Application of a Hybridization-Independent, DNA-Encoded Reaction Discovery System Compatible with Organic Solvents