NNO Pincer-Supported Pd(II)-Catalyzed Reductive N-Alkylation of Challenging Nitroarenes with Alcohols via Borrowing Hydrogen Strategy.

Abstract

A sustainable catalytic synthesis of selective monoalkylated amines from nitroarenes and alcohols by new palladium(II)-NNO pincer-type complexes has been described. Herein, a series of Pd(II) complexes [Pd(NNO)PPh3] (1-3) are synthesized and characterized by analytical and spectroscopic (IR, NMR, and HR-MS) methods. The solid-state molecular structures of two complexes are established by X-ray single-crystal diffraction. Furthermore, the catalytic N-alkylation of challenging nitroarenes with primary and secondary alcohols has been performed by the well-defined palladium(II) complexes via borrowing hydrogen strategy. The current protocol offers a wide range of monoalkylated amines (26 examples) with a maximum yield of 87% utilizing 1 mol % of catalyst loading. Gratifyingly, the catalytic system works well under mild reaction conditions and atom economy with water is the only byproduct. Furthermore, control experiments confirm the formation of probable intermediates (aniline, aldehyde, and imine), and deuterium labeling authenticates the borrowing hydrogen mechanism. A gram-scale synthesis of an alkylated product clearly demonstrates the synthetic efficacy of the present catalytic methodology.