Palladium-catalyzed relay hydroaminocarbonylation of alkenes with hydroxylamine hydrochloride as an ammonia equivalent

Jiawen Li,Siyuan Wang,Hanmin Huang,Suchen Zou

doi:10.1038/s42004-019-0108-5

Abstract

Amides are prevalent in pharmaceuticals, agrochemicals, and materials. Hydroaminocarbonylation of alkenes has emerged as one of the most direct and rapid approaches to amides. Nowadays, these reactions remain largely confined to using alkylamines as nitrogen sources, leading to sluggish reactions due to their strong binding ability and basicity. Here we show the application of abundantly available hydroxylamine hydrochloride (NH2OH·HCl) as a surrogate of ammonia for the relay hydroaminocarbonylation of simple alkenes in the presence of a convenient palladium catalyst system. The in situ formation of alkylamines from hydroxylamine hydrochloride by hydroaminocarbonylation reaction and Lossen rearrangement allows us to establish an efficient relay hydroaminocarbonylation. Notably, this transformation allows the catalytic formation of two C–N bonds with hydroxylamine hydrochloride as an amine source by incorporation of two molecules of alkene and avoids the use of alkylamines.

Highlights

Amides are prevalent in pharmaceuticals, agrochemicals, and materials
Some ammonium salts have been utilized as ammonia surrogates for transition metal-catalyzed C–N bond formation reactions[5,6], yet catalytic reactions between simple alkenes and ammonium salts remain largely unexplored[7]
It is highly desirable to identify an alternative strategy that is capable of producing alkylamines from the simple alkenes and further able to transfer the alkylamines into secondary amides

Summary

Introduction

Amides are prevalent in pharmaceuticals, agrochemicals, and materials. Hydroaminocarbonylation of alkenes has emerged as one of the most direct and rapid approaches to amides. Among the numerous strategies for the preparation of amides, transition metal-catalyzed hydroaminocarbonylation of alkenes has emerged as one of the most promising methods, enabling a rapid access to various amides from abundant and cost-effective feedstock materials[12,13,14,15,16,17,18,19,20,21,22] At present, these catalytic hydrocarbonylative C–N bond formation reactions remain largely confined to the utilization of primary or secondary amines as amine sources (Fig. 1a). To the best of our knowledge, there is currently no reported strategy that is capable of generation of primary amines via hydroamination of unactivated alkenes with simple ammonia in the presence of CO27

Methods

Results

Conclusion