Mild Access to N‐Formylation of Primary Amines using Ethers as C1 Synthons under Metal‐Free Conditions

Abstract

Abstract A new synthetic protocol has been developed for the synthesis of N ‐formamide derivatives using ethers as a C1 synthon under metal‐free reaction conditions. The reaction is proposed to proceed through C−H functionalization, C−O cleavage, and C−N bond formation. This protocol is applicable to a variety of primary amines resulting in N ‐formamides in moderate to good yields. 1,4‐dioxane was chosen as best C1 synthon after screening with various ethers. Mechanistic studies disclosed that the reaction proceeds through a radical pathway. While using α‐amino ketones a α‐alkylation product was formed rather than formylation. By replacing dioxane with Tetramethylethylenediamine (TMEDA) under standard conditions also gave the N ‐formamide derivatives in moderate yields. magnified image