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Keywords = β-thioenamide

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19 pages, 1694 KiB  
Article
Photocatalyzed Oxidative Decarboxylation Forming Aminovinylcysteine Containing Peptides
by Masaya Kumashiro, Kosuke Ohsawa and Takayuki Doi
Catalysts 2022, 12(12), 1615; https://doi.org/10.3390/catal12121615 - 9 Dec 2022
Cited by 3 | Viewed by 3090
Abstract
The formation of (2S,3S)-S-[(Z)-aminovinyl]-3-methyl-D-cysteine (AviMeCys) substructures was developed based on the photocatalyzed-oxidative decarboxylation of lanthionine-bearing peptides. The decarboxylative selenoetherification of the N-hydroxyphthalimide ester, generated in situ, proceeded under mild conditions at −40 °C in [...] Read more.
The formation of (2S,3S)-S-[(Z)-aminovinyl]-3-methyl-D-cysteine (AviMeCys) substructures was developed based on the photocatalyzed-oxidative decarboxylation of lanthionine-bearing peptides. The decarboxylative selenoetherification of the N-hydroxyphthalimide ester, generated in situ, proceeded under mild conditions at −40 °C in the presence of 1 mol% of eosin Y-Na2 as a photocatalyst and the Hantzsch ester. The following β-elimination of the corresponding N,Se-acetal was operated in a one-pot operation, led to AviMeCys substructures found in natural products in moderate to good yields. The sulfide-bridged motif, and also the carbamate-type protecting groups, such as Cbz, Teoc, Boc and Fmoc groups, were tolerant under the reaction conditions. Full article
(This article belongs to the Special Issue Theme Issue in Memory to Prof. Jiro Tsuji (1927–2022))
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