Enantioselective Giese Additions of Prochiral α-Amino Radicals
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American Chemical Society
https://doi.org/10.1021/jacs.2c11367
https://doi.org/10.1021/jacs.2c11367
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Funder: Orionin Tutkimuss??ti?
Funder: Emil Aaltosen S??ti?
Funder: Royal Society
Funder: AstraZeneca
Amines featuring an adjacent stereocenter are important build-ing blocks and recent years have seen remarkable growth in methods forming these via prochiral α-amino radical interme-diates. 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. Incorpora-tion of a removable basic heteroarene into the substrate enables a network of attractive non-covalent 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 antici-pate that this strategy will be applicable to other asymmetric radical transformations.
ERC H2020, AstraZeneca, Royal Society, Isaac-Newton Trust, Orion Research Foundation sr (A.S.K.L) and Emil Aaltonen Foundation
Funder: Emil Aaltosen S??ti?
Funder: Royal Society
Funder: AstraZeneca
Amines featuring an adjacent stereocenter are important build-ing blocks and recent years have seen remarkable growth in methods forming these via prochiral α-amino radical interme-diates. 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. Incorpora-tion of a removable basic heteroarene into the substrate enables a network of attractive non-covalent 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 antici-pate that this strategy will be applicable to other asymmetric radical transformations.
ERC H2020, AstraZeneca, Royal Society, Isaac-Newton Trust, Orion Research Foundation sr (A.S.K.L) and Emil Aaltonen Foundation