Aprotic Deamination of Primary Amines as a Route to Esters

Abstract

Nucleophilic displacements at carbon that replace primary amines with other functionality are useful tools in organic chemistry. Those of any generality are few. The direct deamination of primary amines with nitrous acid has been extensively studied.¹ The reaction yields such a variety of elimination, rearrangement, and substitution products that, in general, it is not a preparatively useful reaction.² The elegant work of White has led to three indirect methods capable of giving substitution in preparatively useful yields and purity, those based on nitrosoamides,³ nitroamides,⁴ and triazines.⁵ Baumgarten has developed a useful method based on the N, N-diarylsulfonyl imide functionality,⁶ and Wudl has reported direct conversion of primary aimes to alkyl nitrates utilizing N₂ O ₄.⁷