Giri, Rahul; Zhilin, Egor; Katayev, Dmitry (2024). Divergent functionalization of alkenes enabled by photoredox activation of CDFA and α-halo carboxylic acids. Chemical Science, 15(27), pp. 10659-10667. The Royal Society of Chemistry 10.1039/d4sc01084a
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Herein we present our studies on the solvent-controlled difunctionalization of alkenes utilizing chlorodifluoroacetic acid (CDFA) and α-halo carboxylic acids for the synthesis of γ-lactones, γ-lactams and α,α-difluoroesters. Mechanistic insights revealed that photocatalytic reductive mesolytic cleavage of the C-X bond delivers elusive α-carboxyl alkyl radicals. In the presence of an olefin molecule, this species acts as a unique bifunctional intermediate allowing for stipulated formation of C-O, C-N and C-H bonds on Giese-type adducts via single electron transfer (SET) or hydrogen atom transfer (HAT) events. These protocols exhibit great efficiency across a broad spectrum of readily available α-halo carboxylic acids and are amenable to scalability in both batch and flow. To demonstrate the versatility of this concept, the synthesis of (±)-boivinianin A, its fluorinated analog and eupomatilone-6 natural products was successfully accomplished.
Item Type: |
Journal Article (Original Article) |
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Division/Institute: |
08 Faculty of Science > Department of Chemistry, Biochemistry and Pharmaceutical Sciences (DCBP) |
UniBE Contributor: |
Giri, Rahul, Zhilin, Egor, Katayev, Dmitry |
Subjects: |
500 Science > 570 Life sciences; biology 500 Science > 540 Chemistry |
ISSN: |
2041-6520 |
Publisher: |
The Royal Society of Chemistry |
Language: |
English |
Submitter: |
Pubmed Import |
Date Deposited: |
17 Jul 2024 09:17 |
Last Modified: |
17 Jul 2024 09:27 |
Publisher DOI: |
10.1039/d4sc01084a |
PubMed ID: |
38994427 |
BORIS DOI: |
10.48350/198972 |
URI: |
https://boris.unibe.ch/id/eprint/198972 |
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