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Journal ArticleDOI

Traditional and New methods for the Preparation of Diazocarbonyl Compounds

16 Apr 2018-Anais Da Academia Brasileira De Ciencias (Academia Brasileira de Ciências)-Vol. 90, Iss: 1, pp 859-893
TL;DR: In this paper, the traditional methods to prepare diazocarbonyl compounds as well as the new methods and recent improvements in experimental procedures are summarized and compared. And the emergence of continuous flow techniques has allowed safer and environmentally friendly procedures for handling diazomethane and diazo compounds and will also be a topic in this review.
Abstract: For many years diazocarbonyl compounds have been studied due to their versatility and usability in many chemical transformations. In this review, we summarize the traditional methods to prepare these compounds as well as the new methods and recent improvements in experimental procedures. Moreover, emergence of continuous flow techniques has allowed safer and environmentally friendly procedures for the handling of diazomethane and diazo compounds and will also be a topic in this review

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Citations
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Journal ArticleDOI
TL;DR: Imidoyl sulfoxonium ylides are presented for the first time as potential precursors to generate α-imino metal-carbene intermediates and applied in direct C-H functionalization reactions catalyzed by [Ir(cod)Cl]2 to provide 2-substituted indoles in just one step.
Abstract: Imidoyl sulfoxonium ylides are presented for the first time as potential precursors to generate α-imino metal-carbene intermediates and applied in direct C-H functionalization reactions catalyzed by [Ir(cod)Cl]2 (4 mol %) to provide 2-substituted indoles (up to 70% yield) in just one step. This class of sulfur ylide is successfully obtained from imidoyl chloride and dimethylsulfoxonium methylide (23 new examples in 45-85% yield) or by imino group formation from the corresponding β-keto sulfoxonium ylides and anilines in the presence of TiCl4 as a Lewis acid (9 examples in 33-94% yield).

36 citations

Journal ArticleDOI
TL;DR: In this paper, the authors used eco-friendly silica-supported HClO4 as the catalyst for solvent-free O-H insertion reactions in the presence of diazo carbonyl compounds.

24 citations

Journal ArticleDOI
TL;DR: Through this method, the successive site-selective conjugation of the triazido molecule with three different components is demonstrated and the selective conversion of alkyl azido groups at the carbonyl α-position to diazo compounds is reported.
Abstract: This paper reports on the selective conversion of alkyl azido groups at the carbonyl α-position to diazo compounds. Through β-elimination of dinitrogen, followed by hydrazone formation/decomposition, α-azidocarbonyl moieties were transformed into α-diazo carbonyl groups in one step. As these reaction conditions do not involve aryl or general alkyl azides, site-selective conversions of di- and triazides were achieved. Through this method, the successive site-selective conjugation of the triazido molecule with three different components is demonstrated.

20 citations

Journal ArticleDOI
TL;DR: An efficient cascade approach to thiosubstituted benzoxazoles has been developed and features very good functional group tolerance and is applicable to substrates with different electronic properties.
Abstract: An efficient cascade approach to thiosubstituted benzoxazoles has been developed. The transformation starts with in situ generation of a diazo compound via annulation-triggered electrocyclic openin...

14 citations

Journal ArticleDOI
03 Jan 2019
TL;DR: A direct synthesis of the rare fused bicyclic [1,2,3]-triazoles is demonstrated, employing γ-N-protected amino diazoketones as useful synthetic platforms and carried out in good to excellent yields.
Abstract: Triazoles are an important class of N-heterocycles that are well known for their broad biological activities. In this work, we would like to demonstrate a direct synthesis of the rare fused bicyclic [1,2,3]-triazoles, employing γ-N-protected amino diazoketones as useful synthetic platforms. The strategy was based on the deprotection of a trifluoroacetamide group for the intramolecular and in situ generation of an α-diazo imine intermediate, followed by a 5-endo-dig cyclization to construct the bicyclic unit. In this fashion, the synthesis of a series of fused bicyclic [1,2,3]-triazoles could be carried out in good to excellent yields (63–95%).

9 citations

References
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Book
19 Jan 1998
TL;DR: Synthesis of Alpha-Diazocarbonyl Compounds Catalysts for Metal Carbene Transformations Insertion Reactions Intermolecular Cyclopropanation and Related Addition Reactions Intramolecular cyclopropaneation and related addition Reactions Cycloaddition and Substitution Reactions with Aromatic and Heteroaromatic Compounds Generation and Reactions of Ylides from DBCs X-H InsertionReactions of DBC compounds (X = N,O,S,Se,P, Halogen) The
Abstract: Synthesis of Alpha-Diazocarbonyl Compounds Catalysts for Metal Carbene Transformations Insertion Reactions Intermolecular Cyclopropanation and Related Addition Reactions Intramolecular Cyclopropanation and Related Addition Reactions Cycloaddition and Substitution Reactions with Aromatic and Heteroaromatic Compounds Generation and Reactions of Ylides from Diazocarbonyl Compounds X-H Insertion Reactions of Diazocarbonyl Compounds (X = N,O,S,Se,P, Halogen) The Wolff Rearrangement and Related Reactions Reactions of Alpha-Diazocarbonyl Compounds with Aldehydes and Ketones Acid-Promoted Cyclization of Unsaturated and Aromatic Diazo Ketones Miscellaneous Diazocarbonyl Reactions Index

1,112 citations


"Traditional and New methods for the..." refers background or methods in this paper

  • ...Thus, several publications with respect to the preparation, properties, and applications in organic chemistry have been published (Doyle et al. 1998, Ford et al. 2015, Maas 2009, Ye and McKervey 1994)....

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  • ...(Doyle et al. 1998) (Figure 30)....

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  • ...Effects of the base and solvent on diazo transfer reactions were also studied by some groups (Doyle et al. 1998)....

    [...]

  • ...Dehydrogenation of hydrazones is one of the oldest methods for the synthesis of diazo compounds (Doyle et al. 1998)....

    [...]

  • ...1) compounds as depicted in Figure 36 (Doyle et al. 1998)....

    [...]

Journal ArticleDOI
TL;DR: This Review discusses recent literature examples of continuous-flow organic synthesis where hazardous reactions or extreme process windows have been employed, with a focus on applications of relevance to the preparation of pharmaceuticals.
Abstract: In the past few years, continuous-flow reactors with channel dimensions in the micro- or millimeter region have found widespread application in organic synthesis. The characteristic properties of these reactors are their exceptionally fast heat and mass transfer. In microstructured devices of this type, virtually instantaneous mixing can be achieved for all but the fastest reactions. Similarly, the accumulation of heat, formation of hot spots, and dangers of thermal runaways can be prevented. As a result of the small reactor volumes, the overall safety of the process is significantly improved, even when harsh reaction conditions are used. Thus, microreactor technology offers a unique way to perform ultrafast, exothermic reactions, and allows the execution of reactions which proceed via highly unstable or even explosive intermediates. This Review discusses recent literature examples of continuous-flow organic synthesis where hazardous reactions or extreme process windows have been employed, with a focus on applications of relevance to the preparation of pharmaceuticals.

1,059 citations

Journal ArticleDOI
TL;DR: This work aims to demonstrate the efforts towards in-situ applicability of EMMARM, which aims to provide real-time information about the physical properties of EMTs and their applications in the context of drug discovery and development.
Abstract: Alan Ford,† Hugues Miel, Aoife Ring,† Catherine N. Slattery,† Anita R. Maguire,*,†,‡ and M. Anthony McKervey* †Department of Chemistry and ‡School of Pharmacy, Analytical and Biological Chemistry Research Facility, Synthesis and Solid State Pharmaceutical Centre, University College Cork, Cork, Ireland Almac Discovery Ltd., David Keir Building, Stranmillis Road, Belfast BT9 5AG, United Kingdom Almac Sciences Ltd., Almac House, 20 Seagoe Industrial Estate, Craigavon BT63 5QD, United Kingdom

1,051 citations

Journal ArticleDOI
TL;DR: The design and synthesis of a new diazotransfer reagent, imidazole-1-sulfonyl azide hydrochloride, are reported, which has proven to equal triflyl azides in its ability to act as a "diazo donor" in the conversion of both primary amines into azides and activated methylene substrates into diazo compounds.

502 citations