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Synergistic Peptide and Gold Catalysis: Enantioselective Addition of Branched Aldehydes to Allenamides.

ABSTRACT: The combination of a peptide catalyst and a gold catalyst is presented for enantioselective addition reactions between branched aldehydes and allenamides. The two catalysts act in concert to provide γ,δ-enamide aldehydes bearing a fully substituted, benzylic stereogenic center - a structural motif common in many natural products and therapeutically active compounds - with good yields and enantioselectivities. The reaction tolerates a variety of alkyl and alkoxy substituted aldehydes and the products can be elaborated into several chiral building blocks bearing either 1,4- or 1,5- functional group relationships. Mechanistic studies showed that the conformational features of the peptide are important for both the catalytic efficiency and stereochemistry, while a balance of acid/base additives is key for ensuring formation of the desired product over undesired side reactions.

SUBMITTER: Nicholls LDM

PROVIDER: S-EPMC9293318 | biostudies-literature | 2021 Dec

REPOSITORIES: biostudies-literature

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Synergistic Peptide and Gold Catalysis: Enantioselective Addition of Branched Aldehydes to Allenamides.

Nicholls Leo D M LDM Wennemers Helma H

Chemistry (Weinheim an der Bergstrasse, Germany) 20211013 70

The combination of a peptide catalyst and a gold catalyst is presented for enantioselective addition reactions between branched aldehydes and allenamides. The two catalysts act in concert to provide γ,δ-enamide aldehydes bearing a fully substituted, benzylic stereogenic center - a structural motif common in many natural products and therapeutically active compounds - with good yields and enantioselectivities. The reaction tolerates a variety of alkyl and alkoxy substituted aldehydes and the prod ...[more]

PMID: 34496089

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