TY - JOUR
T1 - Carboxylate-Assisted Formation of Aryl-Co(III) Masked-Carbenes in Cobalt-Catalyzed C-H Functionalization with Diazo Esters
AU - Planas, Oriol
AU - Roldán-Gómez, Steven
AU - Martin-Diaconescu, Vlad
AU - Parella, Teodor
AU - Luis, Josep M.
AU - Company, Anna
AU - Ribas, Xavi
PY - 2017/10/18
Y1 - 2017/10/18
N2 - © 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.
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.
U2 - 10.1021/jacs.7b07880
DO - 10.1021/jacs.7b07880
M3 - Article
VL - 139
SP - 14649
EP - 14655
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 41
ER -