Diazenes as Powerful and Versatile Tools in Organic Synthesis

Košmrlj, Janez; Kočevar, Marijan; Polanc, Slovenko

doi:10.1055/s-0029-1217553

Cited by 14 publications

(4 citation statements)

References 63 publications

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“…Given the inconsistencies between the theory and experiments, the full mechanistic picture of this transformation remains unclear. Considering these difficulties, there is space for the consideration of other mechanisms that co-opt established diazene-TM chemistry 168 or the variety of organic transformations diazenes are capable of 169 to generate a new type of pseudosymmetric intermediate (Figure 6). Such established diazene-TM chemistry includes several stoichiometric metathesis examples involving dinuclear TM complexes.…”

Section: Metathesismentioning

confidence: 99%

Hetero-ene Metathesis

Johnson,

Zhukhovitskiy

2023

ACS Catal.

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Metathesis of double bonds has enabled innovation in a broad range of fields: from materials science to medicine. However, this chemistry has largely focused on alkenes rather than hetero-enes, or heteroatom-containing double bonds. Yet, the ability to do hetero-ene metathesis could grant access to valuable heteroatom-rich molecules. Catalysis of double bond metathesis has classically, though not exclusively, relied on the [2+2] cycloaddition/elimination mechanism, which in the case of olefins involves transition metal alkylidenes. However, this mechanism may not be ideal for some hetero-enes, nor is it uniquely suited for the purposes of metathesis: other mechanisms are feasible and, in some cases, precedented. In this Perspective, we present a general framework for mechanistic design that would apply to hetero-ene metathesis, with examples of reported transformations that justify this classification. Advantages, challenges, and opportunities within each class of mechanisms are also outlined. We hope that this Perspective will catalyze further research in this burgeoning field.

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Section: Metathesismentioning

confidence: 99%

Hetero-ene Metathesis

Johnson,

Zhukhovitskiy

2023

ACS Catal.

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“…Diazenes have found broad applicability as dyes, pharmaceuticals, − and photoswitches. , They undergo a variety of pericyclic reactions, − can be used as catalysts, and are capable of storing hydrogen . The recently reported syntheses of indoles, amines, , and aldehydes, , as well as the modular formation of C–C bonds, − use alkylaryldiazenes.…”

Section: Introductionmentioning

confidence: 99%

Photoredox-Catalyzed Synthesis of Alkylaryldiazenes: Formal Deformylative C–N Bond Formation with Alkyl Radicals

et al. 2020

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Diazenes are valuable compounds that have found broad applicability because of their optical and biological properties. We report the synthesis of alkylaryldiazenes via formal, photoredox-catalyzed, deformylative C–N bond formation. The procedure employs dihydropyridines for the generation of alkyl radicals, which are then trapped by diazonium salts and reduced to the corresponding diazenes. Control experiments were performed to confirm the involvement of radicals in the mechanism. The reaction can be carried out at room temperature and employs readily available reagents; the mild conditions allowed the use of highly functionalized substrates. There was no observed tautomerization of the diazenes to the corresponding arylhydrazones.

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“…Our research group recently encountered the need to oxidatively prepare azocarboxylate derivatives as part of our efforts to develop strategies for heterocycle synthesis. Azocarboxylates, azobenzenes, and related diazenes have wide utility in a variety of applications, including use as photoswitches and dyes . They are also useful synthetic reagents in their own right: for example, azocarboxylates such as 3 have recently been shown to be effective aryl radical precursors, dienophiles/dipolarophiles, and Mitsunobu reagents .…”

mentioning

confidence: 99%

“…Azocarboxylates, azobenzenes, and related diazenes have wide utility in a variety of applications, including use as photoswitches and dyes. 8 They are also useful synthetic reagents in their own right: for example, azocarboxylates such as 3 have recently been shown to be effective aryl radical precursors, 9 dienophiles/dipolarophiles, 10 and Mitsunobu reagents. 11 Consequently, various approaches to oxidatively synthesize diazenes from the corresponding hydrazides have been developed, the majority of which use stoichiometric oxidants such as Selectfluor, H 2 O 2 , K 3 Fe(CN) 6 , MnO 2 , or N -bromosuccinimide, among others.…”

mentioning

confidence: 99%

Green Oxidation of Aromatic Hydrazide Derivatives Using an Oxoammonium Salt

Phadnis,

Molen,

Stephens

et al. 2024

J. Org. Chem.

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Aromatic diazenes are often prepared by oxidation of the corresponding hydrazides using stoichiometric quantities of nonrecyclable oxidants. We developed a convenient alternative protocol for the oxidation of aromatic hydrazides using Bobbitt's salt (1), a metal-free, recyclable, and commercially available oxoammonium reagent. A variety of aryl hydrazides were oxidized within 75 min at room temperature using the developed protocol. Computational insight suggests that this oxidation occurs by a polar hydride transfer mechanism.

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Diazenes as Powerful and Versatile Tools in Organic Synthesis

Abstract: This account describes the application of diazenes as electrophiles in reactions with alkenes, arenes, aldehydes, ketones, and some other compounds, as well as a variety of transformations that take advantage of the oxidative properties of diazenes.

Cited by 14 publications

References 63 publications

Hetero-ene Metathesis

Hetero-ene Metathesis

Photoredox-Catalyzed Synthesis of Alkylaryldiazenes: Formal Deformylative C–N Bond Formation with Alkyl Radicals

Green Oxidation of Aromatic Hydrazide Derivatives Using an Oxoammonium Salt

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