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Palladium catalyzed carbonylative generation of potent, pyridine-based acylating electrophiles for the functionalization of arenes to ketones.

ABSTRACT: We describe here the design of a palladium catalyzed route to generate aryl ketones via the carbonylative coupling of (hetero)arenes and aryl- or vinyl-triflates. In this, the use of the large bite angle Xantphos ligand on palladium provides a unique avenue to balance the activation of the relatively strong C(sp²)-OTf bond with the ultimate elimination of a new class of potent Friedel-Crafts acylating agent: N-acyl pyridinium salts. The latter can be exploited to modulate reactivity and selectivity in carbonylative arene functionalization chemistry, and allow the efficient synthesis of ketones with a diverse array of (hetero)arenes.

SUBMITTER: Liu Y

PROVIDER: S-EPMC8163404 | biostudies-literature | 2020 Jul

REPOSITORIES: biostudies-literature

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Palladium catalyzed carbonylative generation of potent, pyridine-based acylating electrophiles for the functionalization of arenes to ketones.

Liu Yi Y Kaiser Angela M AM Arndtsen Bruce A BA

Chemical science 20200728 32

We describe here the design of a palladium catalyzed route to generate aryl ketones via the carbonylative coupling of (hetero)arenes and aryl- or vinyl-triflates. In this, the use of the large bite angle Xantphos ligand on palladium provides a unique avenue to balance the activation of the relatively strong C(sp2)-OTf bond with the ultimate elimination of a new class of potent Friedel-Crafts acylating agent: N-acyl pyridinium salts. The latter can be exploited to modulat ...[more]

PMID: 34123121

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