Work

Trapping Reactions of Benzynes Initiated by Intramolecular Nucleophilic Addition of a Carbonyl Oxygen to the Electrophilic Aryne

Year: 2021

Type: article

Abstract: We describe here reactions in which a carbonyl oxygen atom initiates cascade reactions by nucleophilic attack on a covalently attached benzyne. The benzynes are produced by thermal cyclization of triynes via hexadehydro-Diels–Alder reaction. The initially produced oxocarbenium/aryl carbanionic zwitterion is protonated in situ by an external protic nucleophile (NuH) of appropriate acidity. The resulting ion pair (oxocarbenium + /Nu – ) collapses through several different mechanistic manifolds, adding to the diversity of structural classes that can be generated.

Source: Organic Letters

DOI: 10.1021/acs.orglett.1c04110

Authors: Bhavani Shankar Chinta, Sahil Arora, Thomas R. Hoye

Institution: University of Minnesota

Language: English

Topic: Cyclization and Aryne Chemistry

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: green

Funders: National Institutes of Health, National Cancer Institute, National Institute of General Medical Sciences

Awards: Upgrade of a 500 MHz NMR Spectrometer for Applications in Biomedical Research, Synthesis, Structure, and Mechanism of Biorelevant Molecules and Reactions, Cancer Center Support Grant