Peroxidase-induced C–N bond formation via nitroso ene and Diels–Alder reactions

Abstract

The formation of new carbon-nitrogen bonds is indisputably one of the most important tasks in synthetic organic chemistry. Here, nitroso compounds offer a highly interesting reactivity that complements traditional amination...

Enzyme‐Triggered Reactions for the Synthesis of Organic Molecules

“…[17] Recently, the Deska group reported an enzyme-triggered ene-type reaction and an enzyme-triggered [4 + 2]cycloaddition. [18] Both of these reactions utilised a dehydrogenation system that comprised of a horseradish peroxidase (HRP) and a glucose oxidase (GO x ) to oxidise the hydroxylamine substrate, such as 45 and 46, to a reactive nitroso intermediate, which can undergo spontaneous reactions with alkenes or dienes. The enzyme-triggered ene-type cyclisation to form oxazolidinone 47 (Scheme 5c) was initially investigated and incrementally scaled up to gram-scale, while maintaining good yields.…”

Multienzymatic Synthesis of γ‐Lactam Building Blocks from Unsaturated Esters and Hydroxylamine

“…The thus formed nitrosocarbonyl species readily undergo non-enzymatic CÀ N coupling reactions with olefinic and diene moieties in inter-or intramolecular fashion to deliver a range of N-heterocyclic molecular architectures. [9,10] In addition to the wide scope, the robust system was proven to be highly scalable and recyclable, therefore allowing higher yields while improving atom economy. [10] In continuation of the enzymedriven incorporation of nitrogen into heterocyclic building blocks, we envisaged that we could use an extended biocatalytic sequence to introduce the key nitrogen atom from a basic inorganic reagent such as hydroxylamine (Scheme 1).…”

“…[9,10] In addition to the wide scope, the robust system was proven to be highly scalable and recyclable, therefore allowing higher yields while improving atom economy. [10] In continuation of the enzymedriven incorporation of nitrogen into heterocyclic building blocks, we envisaged that we could use an extended biocatalytic sequence to introduce the key nitrogen atom from a basic inorganic reagent such as hydroxylamine (Scheme 1).…”

“…The enzyme‐based system relies on the interplay of horseradish peroxidase (HRP) as oxidizer of the N−O substrates with glucose oxidase (GOx) as activator of aerial oxygen under consumption of D‐glucose. The thus formed nitrosocarbonyl species readily undergo non‐enzymatic C−N coupling reactions with olefinic and diene moieties in inter‐ or intramolecular fashion to deliver a range of N‐heterocyclic molecular architectures [9,10] . In addition to the wide scope, the robust system was proven to be highly scalable and recyclable, therefore allowing higher yields while improving atom economy [10] .…”

Revisiting Horseradish Peroxidase-Catalyzed Aerobic Oxidation of NAD(P)H in the Presence of Mn(II) and Mediators: Application in Catalytic Oxidation

“…19 Recently, HRP has sparked renewed interest in synthetic chemistry. For example, several groups reported the oxyfunctionalization of the C(sp 3 )−H bond, 20 the cyclization/aromatization of N-cyclopropyl-N-alkylanilines, 21 and C−N bond formation 22 by HRP (Scheme 1). Also, HRP was exploited to recycle the oxidized cofactors for catalytic oxidation processes in the presence of mediators by the Laurynenas group and us (Scheme 1).…”