期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 139, 期 41, 页码 14649-14655出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.7b07880
关键词
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资金
- European Research Council [ERC-2011-StG-277801]
- MINECO of Spain [CTQ2016-77989-P, CTQ2014-52525-P, CTQ2015-64436-P]
- Generalitat de Catalunya [2014SGR862, 2014SGR931]
- MECD of Spain
- MINECO of Spain
- ICREA
Herein we describe the synthesis of a family of aryl-Co(III)-carboxylate complexes and their reactivity with ethyl diazoacetate. Crystallographic, full spectroscopic characterization, and theoretical evidence of unique C-metalated arylCo(III) enolate intermediates is provided, unraveling a carboxylate-assisted formation of aryl-Co(III) masked-carbenes. Moreover, additional evidence for an unprecedented Co(III)mediated intramolecular SN2-type C-C bond formation in which the carboxylate moiety acts as a relay is disclosed. This novel strategy is key to tame the hot reactivity of a metastable Co(III)-carbene and elicit C-C coupling products in a productive manner.
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