Creating a Defined Chirality in Amino Acids and Cyclic Dipeptides by Photochemical Deracemization
Abstract: 2,5‐Diketopiperazines are cyclic dipeptides displaying a wide range of applications. Their enantioselective preparation has now been found possible from the respective racemates by a photochemical deracemization (53 examples, 74 % to quantitative yield, 71–99 % ee). A chiral benzophenone catalyst in concert with irradiation at λ=366 nm enables to establish the configuration at the stereogenic carbon atom C6 at will. If other stereogenic centers are present in the diketopiperazines they remain unaffected and a stereochemical editing is possible at a single position. Consecutive reactions, including the conversion into N‐aryl or N‐alkyl amino acids or the reduction to piperazines, occur without compromising the newly created stereogenic center. Transient absorption spectroscopy revealed that the benzophenone catalyst processes one enantiomer of the 2,5‐diketopiperazines preferentially and enables a reversible hydrogen atom transfer that is responsible for the deracemization process. The remarkably long lifetime of the protonated ketyl radical implies a yet unprecedented mode of action.
- Location
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Deutsche Nationalbibliothek Frankfurt am Main
- Extent
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Online-Ressource
- Language
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Englisch
- Bibliographic citation
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Creating a Defined Chirality in Amino Acids and Cyclic Dipeptides by Photochemical Deracemization ; day:18 ; month:10 ; year:2023 ; extent:11
Angewandte Chemie / International edition. International edition ; (18.10.2023) (gesamt 11)
- Creator
- DOI
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10.1002/anie.202313606
- URN
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urn:nbn:de:101:1-2023101915070040628590
- Rights
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Open Access; Der Zugriff auf das Objekt ist unbeschränkt möglich.
- Last update
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14.08.2025, 10:52 AM CEST
Data provider
Deutsche Nationalbibliothek. If you have any questions about the object, please contact the data provider.
Associated
- Großkopf, Johannes
- Plaza, Manuel
- Kutta, Roger Jan
- Nuernberger, Patrick
- Bach, Thorsten
Other Objects (12)
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Advanced Photochemical Avenues to Monodisperse Sequence-Defined Macromolecules
Photochemical O−H Functionalization Reactions of Cyclic Diazoamides
Photochemical O−H Functionalization Reactions of Cyclic Diazoamides
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Creating a Defined Chirality in Amino Acids and Cyclic Dipeptides by Photochemical Deracemization
Photochemical Deracemization of Allenes and Subsequent Chirality Transfer
Photochemical Deracemization of Allenes and Subsequent Chirality Transfer
Advanced Photochemical Avenues to Monodisperse Sequence-Defined Macromolecules
Photochemical O−H Functionalization Reactions of Cyclic Diazoamides
Photochemical O−H Functionalization Reactions of Cyclic Diazoamides
Photochemical Ring Expansion of Cyclic Sulfoximines with Aryl Diazoacetates and Subsequent Diastereoconvergent Oxidation
Chirality, Vol. 3
Chirality, Vol. 1
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Amplification of chirality