Journal
SCIENCE
Volume 362, Issue 6411, Pages 225-+Publisher
AMER ASSOC ADVANCEMENT SCIENCE
DOI: 10.1126/science.aau1777
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Funding
- NSF CAREER award [1654656]
- NIH [R35 GM119812]
- American Chemical Society Petroleum Research Fund
- HHMI Gilliam Fellowship
- NATIONAL INSTITUTE OF GENERAL MEDICAL SCIENCES [R35GM119812] Funding Source: NIH RePORTER
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Single-electron reduction of a carbonyl to a ketyl enables access to a polarity-reversed platform of reactivity for this cornerstone functional group. However, the synthetic utility of the ketyl radical is hindered by the strong reductants necessary for its generation, which also limit its reactivity to net reductive mechanisms. We report a strategy for net redox-neutral generation and reaction of ketyl radicals. The in situ conversion of aldehydes to alpha-acetoxy iodides lowers their reduction potential by more than 1 volt, allowing for milder access to the corresponding ketyl radicals and an oxidative termination event. Upon subjecting these iodides to a dimanganese decacarbonyl precatalyst and visible light irradiation, an atom transfer radical addition (ATRA) mechanism affords a broad scope of vinyl iodide products with high Z-selectivity.
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