Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 21, Issue 51, Pages 18779-18784Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201503987
Keywords
arylation; C-H functionalization; cross-coupling; cross-dehydrogenative coupling; hypervalent iodine
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Funding
- Fundacio ICIQ
- MINECO (Severo Ochoa Excellence Accreditation) [CTQ2013-46705-R, SEV-2013-0319]
- Generalitat de Catalunya [2014 SGR 1192]
- CELLEX Foundation through the CELLEX-ICIQ High-Throughput Experimentation platform
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Building on earlier results, a direct metal-free alpha-arylation of substituted cyclic 1,3-diones using ArI(O2CCF3)(2) reagents has been developed; unlike other arylative approaches, the arylated products retain the iodine substituent ortho to the newly formed C-C bond. The mechanism is explored by using DFT calculations, which show a vanishingly small activation barrier for the C-C bond-forming step. In fact, taking advantage of an efficient in situ hypervalent activation, the iodoarenes are shown to undergo a cross-dehydrogenative C-C coupling at the C-H ortho to the iodine. When Oxone is used as terminal oxidant, the process is found to benefit from a rapid initial formation of the hypervalent ArI(OR)(2) species and the sulfate-accelerated final coupling with a ketone. This method complements the ipso selectivity obtained in the metal-catalyzed alpha-arylation of carbonyl compounds.
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