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Chemoselectivity Switching through Coupled Equilibria

preprint
submitted on 27.05.2020 and posted on 28.05.2020 by Ognjen Miljanic, Thamon Puangsamlee
Complex mixtures are found in biological and petrochemical feedstocks, and in the primordial soup implicated in the origins of life. Reacting individual compounds within these mixtures is challenging because of the difficulty in controlling the chemoselectivity of such reactions. We show that the selectivity of imine oxidation can be controlled within doubly dynamic combinatorial libraries, wherein two coupled equilibria determine whether the most oxidizable aldehyde precursor is made available to the oxidant or sequestered away from it. Under the slow oxidation conditions, the most electron-rich precursor can traverse the shallow energy landscape and its oxidation product dominates the final mixture. Faster oxidation captures the imine mixture composition, favoring the products derived from electron poorer push-pull imines.

Funding

Welch Foundation E-1768

History

Email Address of Submitting Author

miljanic@uh.edu

Institution

University of Houston

Country

USA

ORCID For Submitting Author

0000-0002-7876-9034

Declaration of Conflict of Interest

The authors declare no conflict of interest.

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