Work

N‐Insertion of Diazonium Salts Into Ketone Derivatives

Year: 2025

Type: article

Abstract: We report a new oxidative nitrogen insertion into cyclic ketones using readily available diazonium salts. In the case of indanones, the reaction is promoted by auto‐catalytically generated Brønsted acid and proceeds via sequential α‐diazenylation and ring expansion through an N‐iminoaziridinium intermediate. For less α‐acidic ketones, a complementary strategy employing silyl enol ethers was developed: catalyzed by HNTf 2 , efficient nitrogen insertion occurred into silyl enol ethers derived from a broad range of four‐ to seven‐membered cyclic ketones. The resulting N‐aminoamides exhibit broad synthetic utility in various downstream transformations. Notably, a ring expansion, followed by N─N bond cleavage offers a powerful tool for skeletal editing, converting indanones into isoquinolinones, as demonstrated by the scaffold modification of donepezil.

Source: Angewandte Chemie

DOI: 10.1002/ange.202505341

Authors: Mohammed Anif Pasha, Jiwon Jang, Youngjin Bae, Seunghoon Shin

Institutions: Syngene International (India), Hanyang University

Language: English

Topic: Cyclopropane Reaction Mechanisms

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: hybrid

Estimated APC paid: $5,790

Funders: National Research Foundation of Korea, Korea Drug Development Fund