Enantioselective Giese Additions of Prochiral α-Amino Radicals.

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Lahdenperä, Antti SK 

Amines featuring an adjacent stereocenter are important building blocks, and recent years have seen remarkable growth in methods forming these via prochiral α-amino radical intermediates. However, very few can exert control over the newly formed stereocenter. We disclose a strategy to overcome this in the context of one of the most widely used radical carbon-carbon bond forming reactions, the Giese reaction. Incorporation of a removable basic heteroarene into the substrate enables a network of attractive noncovalent interactions between a phosphoric acid catalyst, the subsequently formed α-amino radical, and the Giese acceptor, allowing the catalyst to exert control during the C-C bond forming step. Deprotection of the products leads to analogues of γ-aminobutyric acid. We anticipate that this strategy will be applicable to other asymmetric radical transformations in which catalyst control is presently challenging.

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J Am Chem Soc
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American Chemical Society (ACS)
Isaac Newton Trust (20.40(i))
Engineering and Physical Sciences Research Council (EP/S03269X/1)
Royal Society (URF\R\191003)
European Research Council (757381)
ERC H2020, AstraZeneca, Royal Society, Isaac-Newton Trust, Orion Research Foundation sr (A.S.K.L) and Emil Aaltonen Foundation