Irradiation of donor-acceptor complexes formed between alpha-chloroamides and the fully reduced flavin mononucleotide (FMN) of old yellow enzymes (OYEs) effects a reductive single electron transfer event that allows for selective alpha-amide radical generation within the confines of the active site. Alpha-amide radicals formed in this way can participate in enantioselective intramolecular C-C bond formations in 5-exo, 6-exo, and 7-exo trig cyclizations to form beta-substituted butyro-, valero-, and caprolactams. Alternatively, enantioselective hydrogen atom transfer (HAT) from flavin occurs in 5-endo and 8-endo trig cyclizations to yield gamma-substituted butyrolactams and azocan-2-ones, respectively. Additionally, 5-exo trig cyclizations onto trisubstituted olefins may combine the stereoselectivities of C-C and C-H bond formation to control the creation of two stereogenic centers in a single chemical step, yielding beta-substituted butyrolactams containing an additional exocyclic center. Taken collectively, these results demonstrate the ability of flavoprotein photobiocatalysis to address longstanding challenges in synthetic radical chemistry.

New stereoselective C-C and C-H bond formations enabled by flavoprotein photocatalysis

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.