Alcohols can be used as solvents, fuels, detergents, plasticizers, and other specialty chemicals. The synthesis of alcohols typically relies on the use of olefins as readily available feedstocks. The direct preparation of alcohols with anti-Markovnikov selectivity from olefins and water is highly sought after due to its atom economy and potential cost-effectiveness. However, the developed methods have been limited to styrenes and olefins with oxidation potentials below 2.0-2.1 V, which excludes most unconjugated olefins from the conversion range. Therefore, achieving direct catalytic anti-Markovnikov hydration reactions across a broad range of olefins remains a significant challenge. Here, the Max Planck Institute for Coal Research Tobias Ritter team proposes a general method for the direct catalytic anti-Markovnikov hydration of unconjugated tri- and disubstituted olefins. This key advancement is attributed to an oxidizing (E*red = 2.15 V) N-H acridinium catalyst, which enables the functionalization of olefins that previously did not react in such transformations due to high oxidation potentials. The developed method is not limited to hydration but can also proceed via the same mechanistic pathway for other hydrogen functionalizations, such as hydrogen etherification reactions.
Figure 1. Synthesis Reaction (Image Source: J. Am. Chem. Soc.)
Figure 2. Reaction Mechanism and Catalyst Development (Image Source: J. Am. Chem. Soc.)
Figure 3. Hydration Reaction Scope (Image Source: J. Am. Chem. Soc.)
Figure 4. Series of Olefin Oxidation Potentials (Image Source: J. Am. Chem. Soc.)
Figure 5. Reactivity with Other Nucleophiles (Image Source: J. Am. Chem. Soc.)
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Paper Information
Boris Alexander van der Worp, Tobias Ritter*. N-Protonated Acridinium Catalyst Enables Anti-Markovnikov Hydration of Unconjugated Tri- and Disubstituted Olefins. J. Am. Chem. Soc., 2025, https://doi.org/10.1021/jacs.4c18185.
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