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Synthesis 2022; 54(02): 341-354
DOI: 10.1055/a-1625-9095
DOI: 10.1055/a-1625-9095
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Native Amine-Directed ortho-C–H Halogenation and Acetoxylation /Condensation of Benzylamines
This work was supported in part through start-up funds from The University of Toledo, as well as a generous grant from the ACS Herman Frasch Foundation for Chemical Research (830-HF17). J.F.K. was supported by funds from The University of Toledo, Office of Undergraduate Research (Undergraduate Summer Research and Creative Activities Program).
Abstract
Free or unfunctionalized benzylamines are well known to participate in C–H activation in the presence of palladium salts. Despite the ease with which these complexes can be activated, subsequent functionalization of the dimeric cyclometalates can be challenging. We demonstrate herein a free primary amine based C–H activation/functionalization protocol that allows for the ortho-C–H chlorination and bromination of unprotected benzylamines. We also demonstrate how use of fluorine-based oxidants gives rise to a unique acetoxylation/cyclization owing to the nucleophilicity of the free primary amine directing group.
Key words
amines - catalysis - halogenation - palladacycles - palladium - oxidation - cyclization - condensationSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-1625-9095.
- Supporting Information
Publication History
Received: 24 August 2021
Accepted: 31 August 2021
Accepted Manuscript online:
31 August 2021
Article published online:
24 September 2021
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