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Divergent Strain-Release Amino-Functionalization of [1.1.1]Propellane with Electrophilic Nitrogen-Radicals |
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| Authors: | Dr. Ji Hye Kim Dr. Alessandro Ruffoni Prof. Yasair S. S. Al-Faiyz Prof. Nadeem S. Sheikh Dr. Daniele Leonori |
| Affiliation: | 1. Department of Chemistry, University of Manchester, Oxford Road, Manchester, M13 9PL UK;2. Department of Chemistry, University of Manchester, Oxford Road, Manchester, M13 9PL UK These authors contributed equally to this work.;3. Department of Chemistry, College of Science, King Faisal University, P.O. Box 380, Al-Ahsa, 31982 Saudi Arabia |
| Abstract: | Herein we report the development of a photocatalytic strategy for the divergent preparation of functionalized bicyclo[1.1.1]pentylamines. This approach exploits, for the first time, the ability of nitrogen-radicals to undergo strain-release reaction with [1.1.1]propellane. This reactivity is facilitated by the electrophilic nature of these open-shell intermediates and the presence of strong polar effects in the transition-state for C−N bond formation/ring-opening. With the aid of a simple reductive quenching photoredox cycle, we have successfully harnessed this novel radical strain-release amination as part of a multicomponent cascade compatible with several external trapping agents. Overall, this radical strategy enables the rapid construction of novel amino-functionalized building blocks with potential application in medicinal chemistry programs as p-substituted aniline bioisosteres. |
| Keywords: | Aminofunktionalisierung Bioisostere Stickstoffradikale Ringspannung |