Copper‐Catalyzed Cyclization and Azidation of γ,δ‐Unsaturated Ketone O‐Benzoyl Oximes

Su, Hailin; Li, Weifei; Xuan, Zhaoli; Yu, Wei

doi:10.1002/adsc.201400681

Cited by 46 publications

(9 citation statements)

References 69 publications

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“…In 2014 Yu and co‐workers reported an intramolecular imination/azidation sequence based on γ,δ‐unsaturated keto‐ o ‐benzoyl oximes (Scheme ) . The catalyst used in this case was CuPF 6 , together with a β‐keto ester ligand.…”

Section: Base‐metal‐catalysed Azidation Reactionsmentioning

confidence: 99%

Metal‐Catalysed Azidation of Organic Molecules

Goswami

Bruin

2016

Eur J Org Chem

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The azide moiety is a desirable functionality in organic molecules, useful in a variety of transformations such as olefin aziridination, C–H bond amination, isocyanate synthesis, the Staudinger reaction and the formation of azo compounds. To harness the versatility of the azide functionality fully it is important that these compounds be easy to prepare, in a clean and cost‐effective manner. Conventional (non‐catalysed) methods to synthesise azides generally require quite harsh reaction conditions that are often not tolerant of functional groups. In the last decade, several metal‐catalysed azidations have been developed in attempts to circumvent this problem. These methods are generally faster, cleaner and more functional‐group‐tolerant than conventional methods to prepare azides, and can sometimes even be conveniently combined with one‐pot follow‐up transformations of the installed azide moiety. This review highlights metal‐catalysed approaches to azide synthesis, with a focus on the substrate scopes and mechanisms, as well as on advantages and disadvantages of the methods. Overall, metal‐catalysed azidation reactions provide shorter routes to a variety of potentially useful organic molecules containing the azide moiety.

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Section: Base‐metal‐catalysed Azidation Reactionsmentioning

confidence: 99%

Metal‐Catalysed Azidation of Organic Molecules

Goswami

Bruin

2016

Eur J Org Chem

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“…In 1999, Narasaka et al reported a palladium-catalyzed intramolecular amino-Heck reaction involving oxidative addition of oxime esters to palladium(0) species as a landmark study. Many transformation reactions using this concept have since been reported. , Recently, a few distinguished mechanistic studies have reported that the involvement of the oxidative addition of oxime esters to palladium(0) was confirmed by the isolation of oxidative adducts. , Although other transition metals such as rhodium, copper, nickel, ruthenium, and iridium have also been studied in terms of their use as a catalyst in similar reactions, − there have been no reports on the isolation of the intermediate complexes of these transition metals.…”

Section: Introductionmentioning

confidence: 99%

C–H Activation Induced by Oxidative Addition of N–O Bonds in Oxime Esters: Formation of Rhodacycles and Cycloaddition with Alkynes

2016

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The reaction of oxime esters with a rhodium(I) precursor to form five-membered rhodacycles via N−O bond cleavage followed by C−H bond activation has been investigated by isolating these complexes. Kinetic studies on the formation of rhodacycles show that the reversible oxidative addition of the N−O bond in the oxime ester to RhCl(PPh 3 ) 3 occurs at room temperature. The E-isomer of the oxime ester was found to undergo rhodacycle formation faster than the Z-isomer, which suggests that the geometry of the oxime esters reflects the geometry of intermediates during C−H activation. The rhodacycle reacted with an alkyne to construct an isoquinoline ring in both stoichiometric and catalytic conditions, despite its basic stability in air, in moisture, and even during heating, which demonstrates the potential of the rhodacycle as an intermediate for further catalytic transformation of oxime esters.

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“…The reaction afforded the corresponding azide containing dihydropyrrole 118 in moderate to good yields (Scheme 30). 140 Mechanistically, this reaction proceeds via either the initial formation of iminyl radicals and its rapid 5-exo cyclization followed by Cumediated azidation of carbon radicals (path a) or the oxidative addition of Cu(I) into N−O bond and subsequent 5-exo cyclization and azidation sequence (path b).…”

Section: Rearomatization Along With the Extrusion Of Somentioning

confidence: 99%

New Strategies for the Synthesis of Aliphatic Azides

2021

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Aliphatic azides are a versatile class of compounds found in a variety of biologically active pharmaceuticals. These compounds are also recognized as useful precursors for the synthesis of a range of nitrogen-based scaffolds of therapeutic drugs, biologically active compounds, and functional materials. In light of the growing importance of aliphatic azides in both chemical and biological sciences, a vast array of synthetic strategies for the preparation of structurally diverse aliphatic azides have been developed over the past decades. However, to date, this topic has not been the subject of a dedicated review. This review aims to provide a concise overview of modern synthetic strategies to access aliphatic azides that have emerged since 2010. The discussed azidation reactions include (a) azidation of C–C multiple bonds, (b) azidation of C–H bonds, (c) the direct transformation of vinyl azides into other aliphatic azides, and (d) miscellaneous reactions to access aliphatic azides. We critically discuss the synthetic outcomes and the generality and uniqueness of the different mechanistic rationale of each of the selected reactions. The challenges and potential opportunities of the topic are outlined.

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Copper‐Catalyzed Cyclization and Azidation of γ,δ‐Unsaturated Ketone O‐Benzoyl Oximes

Cited by 46 publications

References 69 publications

Metal‐Catalysed Azidation of Organic Molecules

Metal‐Catalysed Azidation of Organic Molecules

C–H Activation Induced by Oxidative Addition of N–O Bonds in Oxime Esters: Formation of Rhodacycles and Cycloaddition with Alkynes

New Strategies for the Synthesis of Aliphatic Azides

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