Carboxylate-Assisted Formation of Aryl-Co(III) Masked-Carbenes in Cobalt-Catalyzed C-H Functionalization with Diazo Esters

Oriol Planas; Steven Roldán-Gómez; Vlad Martin-Diaconescu; Teodor Parella; Josep M. Luis; Anna Company; Xavi Ribas

doi:10.1021/jacs.7b07880

Carboxylate-Assisted Formation of Aryl-Co(III) Masked-Carbenes in Cobalt-Catalyzed C-H Functionalization with Diazo Esters

Oriol Planas, Steven Roldán-Gómez, Vlad Martin-Diaconescu, Teodor Parella, Josep M. Luis, Anna Company, Xavi Ribas

Research output: Contribution to journal › Article › Research › peer-review

17 Citations (Scopus)

Abstract

© 2017 American Chemical Society. 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 aryl-Co(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.

Original language	English
Pages (from-to)	14649-14655
Journal	Journal of the American Chemical Society
Volume	139
Issue number	41
DOIs	https://doi.org/10.1021/jacs.7b07880
Publication status	Published - 18 Oct 2017

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title = "Carboxylate-Assisted Formation of Aryl-Co(III) Masked-Carbenes in Cobalt-Catalyzed C-H Functionalization with Diazo Esters",

abstract = "{\textcopyright} 2017 American Chemical Society. 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 aryl-Co(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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Carboxylate-Assisted Formation of Aryl-Co(III) Masked-Carbenes in Cobalt-Catalyzed C-H Functionalization with Diazo Esters. / Planas, Oriol; Roldán-Gómez, Steven; Martin-Diaconescu, Vlad; Parella, Teodor; Luis, Josep M.; Company, Anna; Ribas, Xavi.

In: Journal of the American Chemical Society, Vol. 139, No. 41, 18.10.2017, p. 14649-14655.

Research output: Contribution to journal › Article › Research › peer-review

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AU - Martin-Diaconescu, Vlad

AU - Parella, Teodor

AU - Luis, Josep M.

AU - Company, Anna

AU - Ribas, Xavi

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Y1 - 2017/10/18

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AB - © 2017 American Chemical Society. 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 aryl-Co(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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