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Lewis acid enhancement by hydrogen-bond donors for asymmetric catalysis.

ABSTRACT: Small-molecule dual hydrogen-bond (H-bond) donors such as ureas, thioureas, squaramides, and guanidinium ions enjoy widespread use as effective catalysts for promoting a variety of enantioselective reactions. However, these catalysts are only weakly acidic and therefore require highly reactive electrophilic substrates to be effective. We introduce here a mode of catalytic activity with chiral H-bond donors that enables enantioselective reactions of relatively unreactive electrophiles. Squaramides are shown to interact with silyl triflates by binding the triflate counterion to form a stable, yet highly Lewis acidic, complex. The silyl triflate-chiral squaramide combination promotes the generation of oxocarbenium intermediates from acetal substrates at low temperatures. Enantioselectivity in nucleophile additions to the cationic intermediates is then controlled through a network of noncovalent interactions between the squaramide catalyst and the oxocarbenium triflate.

SUBMITTER: Banik SM

PROVIDER: S-EPMC5728151 | biostudies-literature | 2017 Nov

REPOSITORIES: biostudies-literature

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Lewis acid enhancement by hydrogen-bond donors for asymmetric catalysis.

Banik Steven M SM Banik Steven M SM Levina Anna A Hyde Alan M AM Jacobsen Eric N EN

Science (New York, N.Y.) 20171101 6364

Small-molecule dual hydrogen-bond (H-bond) donors such as ureas, thioureas, squaramides, and guanidinium ions enjoy widespread use as effective catalysts for promoting a variety of enantioselective reactions. However, these catalysts are only weakly acidic and therefore require highly reactive electrophilic substrates to be effective. We introduce here a mode of catalytic activity with chiral H-bond donors that enables enantioselective reactions of relatively unreactive electrophiles. Squaramide ...[more]

PMID: 29123063

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