Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 143, Issue 4, Pages 1728-1734Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.0c11209
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Funding
- National Institutes of Health (NIH) [R35 GM119652]
- National Science Foundation (NSF) CAREER Award [CHE1848463]
- NIGMS equipment administrative supplement
- Shimadzu Scientific Instruments grant
- Office of the Vice President for Research at Stony Brook University
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The study presents the first excited-state palladium-catalyzed 1,2-spin-center shift reaction for site-selective functionalization of carbohydrates. The strategy offers mild reaction conditions with high levels of selectivity, tolerating a wide range of functional groups and complex molecular architectures, suggesting a general approach for the rapid generation of natural and unnatural carbohydrates.
Excited-state catalysis, a process that involves one or more excited catalytic species, has emerged as a powerful tool in organic synthesis because it allows access to the excited-state reaction landscape for the discovery of novel chemical reactivity. Herein, we report the first excited-state palladium-catalyzed 1,2-spin-center shift reaction that enables site-selective functionalization of carbohydrates. The strategy features mild reaction conditions with high levels of regio- and stereoselectivity that tolerate a wide range of functional groups and complex molecular architectures. Mechanistic studies suggest a radical mechanism involving the formation of hybrid palladium species that undergoes a 1,2-spin-center shift followed by the reduction, deuteration, and iodination to afford functionalized 2-deoxy sugars. The new reactivity will provide a general approach for the rapid generation of natural and unnatural carbohydrates.
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