Abstract
Despite their significant potential, catalytic asymmetric reactions of olefins with formaldehyde are rare and metal-free approaches have not been previously disclosed. Here we describe an enantioselective intermolecular Prins reaction of styrenes and paraformaldehyde to form 1,3-dioxanes, using confined imino-imidodiphosphate (iIDP) Brønsted acid catalysts. Isotope labeling experiments and computations suggest a concerted, highly asynchronous addition of an acid-activated formaldehyde oligomer to the olefin. The enantioenriched 1,3-dioxanes can be transformed into the corresponding optically active 1,3-diols, which are valuable synthetic building blocks.
Highlights
Despite their significant potential, catalytic asymmetric reactions of olefins with formaldehyde are rare and metal-free approaches have not been previously disclosed
The reactions of olefins and aldehydes have earned a coveted spot in the repertoire of the chemist due to the widespread occurrence of these two functional groups
Encouraged by our previous studies on catalytic asymmetric Prins cyclizations,[17] we became intrigued by the possibility to design an enantioselective intermolecular version of this type of olefinaldehyde reaction from readily available substrates (Figure 1B)
Summary
The authors recognize the generous support from the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation, Leibniz Award to B.L.) and under Germany’s. Excellence Strategy (EXC 2033-390677874-RESOLV), the European Research Council (ERC, European Union’s Horizon 2020 research and innovation program “C−H Acids for Organic Synthesis, CHAOS” Advanced Grant Agreement No. Postdoctoral Fellowship (to R.M., Grant Agreement No. 897130). We thank several members of the group for proofreading, and B. Mitschke for the help designing some of the graphics in this manuscript, as well as the technicians of our group and the members of our NMR, MS, and chromatography groups for their excellent service
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