Isolation of Key Organometallic Aryl-Co(III) Intermediates in Cobalt-Catalyzed C(sp2)–H Functionalizations and New Insights into Alkyne Annulation Reaction Mechanisms

PLANAS, Oriol, WHITEOAK, Christopher, MARTIN-DIACONESCU, Vlad, GAMBA, Ilaria, LUIS, Josep M., PARELLA, Teodor, COMPANY, Anna and RIBAS, Xavi (2016). Isolation of Key Organometallic Aryl-Co(III) Intermediates in Cobalt-Catalyzed C(sp2)–H Functionalizations and New Insights into Alkyne Annulation Reaction Mechanisms. Journal of the American Chemical Society, 138 (43), 14388-14397.

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Official URL: http://pubs.acs.org/doi/abs/10.1021/jacs.6b08593
Link to published version:: 10.1021/jacs.6b08593

Abstract

The selective annulation reaction of alkynes with substrates containing inert C–H bonds using cobalt as catalyst is currently a topic attracting significant interest. Unfortunately, the mechanism of this transformation is still relatively poorly understood, with little experimental evidence for intermediates, although an organometallic Co(III) species is generally implicated. Herein, we describe a rare example of the preparation and characterization of benchtop-stable organometallic aryl-Co(III) compounds (NMR, HRMS, XAS, and XRD) prepared through a C(sp2)–H activation, using a model macrocyclic arene substrate. Furthermore, we provide crystallographic evidence of an organometallic aryl-Co(III) intermediate proposed in 8-aminoquinoline-directed Co-catalyzed C–H activation processes. Subsequent insights obtained from the application of our new organometallic aryl-Co(III) compounds in alkyne annulation reactions are also disclosed. Evidence obtained from the resulting regioselectivity of the annulation reactions and DFT studies indicates that a mechanism involving an organometallic aryl-Co(III)-alkynyl intermediate species is preferred for terminal alkynes, in contrast to the generally accepted migratory insertion pathway.

Item Type: Article
Research Institute, Centre or Group: Biomolecular Sciences Research Centre
Identification Number: 10.1021/jacs.6b08593
Depositing User: Christopher Whiteoak
Date Deposited: 02 Nov 2016 09:34
Last Modified: 03 Nov 2016 20:53
URI: http://shura.shu.ac.uk/id/eprint/13911

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