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. 2023 Sep 29;25(38):6969-6974.
doi: 10.1021/acs.orglett.3c02394. Epub 2023 Sep 5.

Nickel Catalyzed Carbonylation/Carboxylation Sequence via Double CO2 Incorporation

Riccardo Giovanelli  1   2 , Lorenzo Lombardi  1 , Riccardo Pedrazzani  1   2 , Magda Monari  1   2 , Marta Castiñeira Reis  3 , Carlos Silva López  3 , Giulio Bertuzzi  1   2 , Marco Bandini  1   2
Affiliations

Nickel Catalyzed Carbonylation/Carboxylation Sequence via Double CO2 Incorporation

Riccardo Giovanelli et al. Org Lett. .

Abstract

A carbonylation-carboxylation synthetic sequence, via double CO2 fixation, is described. The productive merger of a Ni-catalyzed cross-electrophile coupling manifold, with the use of AlCl3, triggered a cascade reaction with the formation of three consecutive C-C bonds in a single operation. This strategy traces an unprecedented synthetic route to ketones under Lewis acid assisted carbon dioxide valorization. Computational insights revealed a unique double function of AlCl3, and labeling (13CO2) experiments validate the genuine incorporation of CO2 in both functional groups.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
(a) State of the art on the use of “CO2≡CO” as C1 synthon in organic synthesis. (b) “Vacancy” on the direct use of CO2 for the catalytic synthesis of ketones. (c) The present working idea ([Mred] and [Mox] indicate different oxidation states of the metal catalyst, [H]: reductant).
Scheme 1
Scheme 1. Scope of the Carbonylation/Carboxylation Reaction
mmol scale reaction.
Scheme 2
Scheme 2. Proving the Synthetic Versatility of Tetralone 2a
Scheme 3
Scheme 3. Top: Proposed Mechanism for the Formation of 2a; Bottom: Proving the Double CO2 Incorporation via Labelling Experiments
Relative Gibbs free energies are expressed in kcal/mol. Oxygen atoms coordinated to AlCl3 are depicted in red.
See this image and copyright information in PMC

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