Autotandem Catalyst: From Acylhydrazones to N', N'-Methylaliphatic Acylhydrazides via Transfer Hydrogenation/ N-Methylation with Methanol Catalyzed by a Cp* Iridium Complex Bearing a Functional Ligand

Shiyuan Luo; Xiangchao Xu; Peng Zhang; Qixun Shi; Xiaoguang Yang; Feng Li

doi:10.1021/acs.orglett.2c03719

Autotandem Catalyst: From Acylhydrazones to N', N'-Methylaliphatic Acylhydrazides via Transfer Hydrogenation/ N-Methylation with Methanol Catalyzed by a Cp* Iridium Complex Bearing a Functional Ligand

Org Lett. 2022 Dec 16;24(49):9081-9085. doi: 10.1021/acs.orglett.2c03719. Epub 2022 Dec 2.

Authors

Shiyuan Luo¹, Xiangchao Xu¹, Peng Zhang², Qixun Shi², Xiaoguang Yang¹, Feng Li¹

Affiliations

¹ School of Chemistry and Chemical Engineering, Nanjing University of Science & Technology, Nanjing 210094, P. R. China.
² Institute of Advanced Synthesis, School of Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing 211816, P. R. China.

PMID: 36459690
DOI: 10.1021/acs.orglett.2c03719

Abstract

A new strategy for the synthesis of N',N'-methylaliphatic acylhydrazides from acylhydrazones via transfer hydrogenation/N-methylation with methanol as both the hydrogen source and the methylating reagent has been proposed and accomplished. In the presence of [Cp*Ir(2,2'-bpyO)(H₂O)] (1 mol %) and Cs₂CO₃ (0.3 equiv), a range of desired products were obtained in high yields. It was also confirmed that functional units in the bpy ligand of the catalyst are crucial for the catalytic activity of iridium complexes. The mechanistic investigation and practical application of the present catalytic system were also presented.