Carboxyboronate as a Versatile In Situ CO Surrogate in Palladium-Catalyzed Carbonylative Transformations

Chieh-Hung Tien; Alina Trofimova; Aleksandra Holownia; Branden S Kwak; Reed T Larson; Andrei K Yudin

doi:10.1002/anie.202010211

Carboxyboronate as a Versatile In Situ CO Surrogate in Palladium-Catalyzed Carbonylative Transformations

Angew Chem Int Ed Engl. 2021 Feb 19;60(8):4342-4349. doi: 10.1002/anie.202010211. Epub 2020 Dec 23.

Authors

Chieh-Hung Tien¹, Alina Trofimova¹, Aleksandra Holownia¹, Branden S Kwak¹, Reed T Larson², Andrei K Yudin¹

Affiliations

¹ Davenport Research Laboratories, Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, ON, M5S 3H6, Canada.
² Process Research & Development, Merck & Co., Inc., Rahway, NJ, 07065, USA.

PMID: 33085182
DOI: 10.1002/anie.202010211

Abstract

The application of carboxy-MIDA-boronate (MIDA=N-methyliminodiacetic acid) as an in situ CO surrogate for various palladium-catalyzed transformations is described. Carboxy-MIDA-boronate was previously shown to be a bench-stable boron-containing building block for the synthesis of borylated heterocycles. The present study demonstrates that, in addition to its utility as a precursor to heterocycle synthesis, carboxy-MIDA-boronate is an excellent in situ CO surrogate that is tolerant of reactive functionalities such as amines, alcohols, and carbon-based nucleophiles. Its wide functional-group compatibility is highlighted in the palladium-catalyzed aminocarbonylation, alkoxycarbonylation, carbonylative Sonogashira coupling, and carbonylative Suzuki-Miyaura coupling of aryl halides. A variety of amides, esters, (hetero)aromatic ynones, and bis(hetero)aryl ketones were synthesized in good-to-excellent yields in a one-pot fashion.

Keywords: C1 building blocks; CO surrogates; carbonylation; carboxyboronates; palladium catalysis.

Abstract

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