Ruthenium(ii)-catalyzed reductive N–O bond cleavage ofN-OR (R = H, alkyl, or acyl) substituted amides and sulfonamides

Abstract

A convenient method for the reductive cleavage of the N–O bonds of amide derivatives was developed using ruthenium(ii)-catalyzed transfer hydrogenation reaction.

Organophotocatalytic N–O Bond Cleavage of Weinreb Amides: Mechanism-Guided Evolution of a PET to ConPET Platform

“…This is noteworthy given the difficulties associated with selective monoalkylation of primary amides and the attractiveness of reductive deprotection. The current suite of methods includes base-mediated elimination approaches and metal-reducing agents that enable single-electron-transfer (SET) processes: examples of the latter include samarium diiodide (N–OBn), lithium (DTBB/NH 3 ), sodium, ruthenium (Zn–Cu), and titanium reagents (Figure C). A metal-free alternative has also been demonstrated using a super electron donor . Although metal-based SET methods constitute the vanguard of N–O bond cleavage platforms, this dominance must be reconciled with limited functional group compatibility and operational challenges.…”

Metal-Free C–H Sulfamidation of 1,4-Naphthoquinone in Water

“…Because of the inherent stability of the amine surrogate, the construction of the Csp 2 –N bond through N–O bond cleavage has been privileged as an important strategy in the amination reaction. Traditionally, expensive and toxic transition-metal catalysts in the presence of specific ligands are utilized for C–H amination through N–O bond cleavage . March and Engenito first reported the metal-free direct amidation of electron-rich arenes by hydroxamic acid using an excess of polyphosphoric acid (PPA) via N–O bond cleavage (Scheme a) .…”

Primary Amination of Ar2P(O)–H with (NH4)2CO3 as an Ammonia Source under Simple and Mild Conditions and Its Extension to the Construction of Various P–N or P–O Bonds

“…Primary amides are useful synthons and serve as versatile precursors in various chemistry transformations . Thus, several strategies for the synthesis of primary amides have been accomplished, including the reduction of nitrilesand the amidation of carboxylic acid derivatives . However, the strategy for the synthesis of primary phosphinamides is still restricted, in spite of the important application of primary phosphinamides in pharmaceuticals, pesticides, or the preparation of organic light-emitting diode as starting materials .…”