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. 2022 Dec 12;61(50):e202210772.
doi: 10.1002/anie.202210772. Epub 2022 Nov 10.

Cobalt-Catalyzed Deaminative Amino- and Alkoxycarbonylation of Aryl Trialkylammonium Salts Promoted by Visible Light

Alexander M Veatch  1 , Shubin Liu  1   2 , Erik J Alexanian  1
Affiliations

Cobalt-Catalyzed Deaminative Amino- and Alkoxycarbonylation of Aryl Trialkylammonium Salts Promoted by Visible Light

Alexander M Veatch et al. Angew Chem Int Ed Engl. .

Abstract

Catalytic carbonylations of aryl electrophiles via C(sp2 )-N cleavage remains a significant challenge. Herein, we demonstrate an aminocarbonylation of aniline-derived trialkylammonium salts promoted by visible light with a simple cobalt catalyst. The reaction proceeds under mild conditions suitable for late-stage functionalization and is amenable to telescoped carbonylations directly from anilines. A range of alkylamines are successful partners, and alkoxycarbonylation is also demonstrated. Mechanistic studies and DFT calculations support a novel mechanism for catalytic carbonylations of aryl electrophiles involving a key visible light-induced carbonyl photodissociation.

Keywords: Amines; Carbonylation; Cobalt; Synthetic Methods; Visible Light.

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Figures

Figure 1.
Figure 1.
Aminocarbonylations of aryl electrophiles.
Figure 2.
Figure 2.
Cobalt-catalyzed aminocarbonylation of aryl trialkylammonium salts with piperidine as the nucleophile. [a] Telescoped reaction from primary aniline. [b] 3 equiv CsF used as base. [c] 10 mol % Co2(CO)8 used as catalyst. [d] Telescoped reaction from secondary aniline. [e] Telescoped reaction from tertiary aniline.
Figure 3.
Figure 3.
Cobalt-catalyzed aminocarbonylation of 4 using diverse amine nucleophiles. [a] 10 mol % Co2(CO)8 as catalyst with 8.0 equiv of CsF as base and 5.0 equiv of amine nucleophile. [b] Ammonium carbamate used as an ammonia surrogate.
Figure 4.
Figure 4.
Cobalt-catalyzed alkoxycarbonylation of 4 using alcohol nucleophiles. [a] 1.3 equiv of trifluoroethanol used as nucleophile. [b] Yield determined by GC with internal standard.
Scheme 1.
Scheme 1.
Telescoped catalytic aminocarbonylation of an aniline used for organocatalyzed enantioselective alkylation.
Scheme 2.
Scheme 2.
Aminocarbonylation mechanism involving photochemical charge transfer of a donor-acceptor complex.
Figure 5.
Figure 5.
DFT-computed free energy profile of the aminocarbonylation with M06–2X/6–311+G(d)/CPCM(2-methyl-2-butanol) level of theory using ammonium salt 8 as the substrate. Energies are relative to the η2 cobalt-arene coordination complex IM1. Analogous activation pathway involving bromobenzene instead of 8 is shown in blue. Optimized structures of selected intermediates and transition states are also shown. See Supplementary Information for a complete free energy profile and alternative pathways. HNR2 = piperidine
Scheme 3.
Scheme 3.
Proposed catalytic cycle for the cobaltate-catalyzed photochemical aminocarbonylation involving CO photodissociation and concerted SNAr C(sp2)–N activation.
See this image and copyright information in PMC

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