Activation of olefins via asymmetric Brønsted acid catalysis

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Science  30 Mar 2018:
Vol. 359, Issue 6383, pp. 1501-1505
DOI: 10.1126/science.aaq0445

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Attacking olefins with chiral acids

A little acid can accelerate a wide range of chemical reactions. The advent of chiral phosphoric acid derivatives has been useful for biasing these reactions toward just one of two mirror-image products. For the most part, though, these chiral catalysts have interacted with basic sites such as carbonyl groups. Tsuji et al. now extend asymmetric acid catalysis to simple carbon-carbon double bonds. Their custom imidodiphosphate forms a pocket that orients olefins to achieve mainly intramolecular alkoxylation on just one face after protonation.

Science, this issue p. 1501


The activation of olefins for asymmetric chemical synthesis traditionally relies on transition metal catalysts. In contrast, biological enzymes with Brønsted acidic sites of appropriate strength can protonate olefins and thereby generate carbocations that ultimately react to form natural products. Although chemists have recently designed chiral Brønsted acid catalysts to activate imines and carbonyl compounds, mimicking these enzymes to protonate simple olefins that then engage in asymmetric catalytic reactions has remained a substantial synthetic challenge. Here, we show that a class of confined and strong chiral Brønsted acids enables the catalytic asymmetric intramolecular hydroalkoxylation of unbiased olefins. The methodology gives rapid access to biologically active 1,1-disubstituted tetrahydrofurans, including (–)-Boivinianin A.

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