Creating a Defined Chirality in Amino Acids and Cyclic Dipeptides by Photochemical Deracemization

Johannes Großkopf, Manuel Plaza, Roger Jan Kutta, Patrick Nuernberger, Thorsten Bach

Publikation: Beitrag in FachzeitschriftArtikelBegutachtung

1 Zitat (Scopus)

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.

OriginalspracheEnglisch
Aufsatznummere202313606
FachzeitschriftAngewandte Chemie International Edition in English
Jahrgang62
Ausgabenummer47
DOIs
PublikationsstatusVeröffentlicht - 20 Nov. 2023

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