Work

A Rapid Injection NMR Study of the Reaction of Organolithium Reagents with Esters, Amides, and Ketones

Year: 2015

Type: article

Abstract: Unexpectedly high rates of reaction between alkyllithium reagents and amides, compared to esters and ketones, were observed by Rapid Inject NMR and competition experiments. Spectroscopic investigations with 4-fluorophenyllithium (ArLi, mixture of monomer and dimer in THF) and a benzoate ester identified two reactive intermediates, a homodimer of the tetrahedral intermediate, stable below -100 °C, and a mixed dimer with ArLi. Direct formation of dimers suggested that the ArLi dimer may be the reactive aggregate rather than the usually more reactive monomer. In contrast, RINMR experiments with ketones demonstrated that the ArLi monomer was the reactive species.

Source: Organic Letters

DOI: 10.1021/acs.orglett.5b00650

Authors: Kristin N. Plessel, Amanda C. Jones, Daniel J. Wherritt, Rebecca M. Maksymowicz, EricT. Poweleit, Hans J. Reich

Institutions: University of Wisconsin System, University of Wisconsin–Madison

Language: English

Topic: Coordination Chemistry and Organometallics

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: hybrid

Estimated APC paid: $4,500

Funders: National Science Foundation, Division of Chemistry