Modern Organic Synthesis with α-Diazocarbonyl Compounds

Ford, Alan; Miel, Hugues; Ring, Aoife; Slattery, Catherine N.; Maguire, Anita R.; McKervey, M. Anthony

doi:10.1021/acs.chemrev.5b00121

Cited by 1,373 publications

(635 citation statements)

References 838 publications

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“…In this context, metal carbene species are interesting reactive intermediates, as they display both nucleophilic and electrophilic reactivity on a single carbon atom and can be easily generated from α-diazo carbonyl compounds. 11 They have been used in a broad range of transformations such as X-H bond insertions, cyclopropanation, ylide formation and 1,2-migration reactions and have been successfully applied in total synthesis. 12 Recently, research in the area has focused on the development of multi-component reactions to afford products with high structural diversity, complexity, and atom economy (Scheme 1B).…”

Section: Scheme 1 Alkynylation Strategies and Multi-component Reactimentioning

confidence: 99%

Copper-Catalyzed Oxy-Alkynylation of Diazo Compounds with Hypervalent Iodine Reagents

2016

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Alkynes have found widespread applications in synthetic chemistry, biology and materials sciences. In recent years, methods based on electrophilic alkynylation with hypervalent iodine reagents have made acetylene synthesis more flexible and efficient, but they lead to the formation of one equivalent of an iodoarene as side-product. Herein, a more efficient strategy involving a copper-catalyzed oxy-alkynylation of diazo compounds with ethynylbenziodoxol(on)e (EBX) reagents is described, which proceeds with generation of nitrogen gas as the only waste. This reaction is remarkable for its broad scope in both EBX reagents and diazo compounds. In addition, vinyl diazo compounds gave enynes selectively as single geometric isomers. The functional groups introduced during the transformation served as easy handles to access useful building blocks for synthetic and medicinal chemistry.The carbon-carbon triple bond is among the most valuable functional groups in organic chemistry because of its versatile reactivity. 1 Alkynes are broadly applied as chemical building blocks for the synthesis of fine chemicals. 2 In past years, they have also gained a lot of interest for applications in biochemistry or material sciences. 1,3 As a result of this growing importance of alkynes, developing more efficient and versatile methods for their synthesis is of fundamental importance. Alkynes are often accessed by the addition of acetylides on electrophilic positions of molecules. 4 However, introducing triple bonds only to electrophilic positions strongly limits the flexibility and efficiency of alkyne synthesis. Major efforts have therefore been made to develop electrophilic alkynylation methods, relying on the umpolung of the innate reactivity of acetylenes (Scheme 1A). 5 Hypervalent iodine reagents such as alkynyliodonium salts have been particularly successful for the electrophilic alkynylation of nucleophiles. 6 However, the use of alkynyliodonium salts is limited due to their low stability. Recently, EthynylBenziodoXol(on)es (EBX) 7a,b have been introduced as excellent electrophilic reagents for the alkynylation of ketoesters, 7c thiols, 7d and aromatic C-H bonds using transition metal catalysis, 7e-g among many other successful transformations. 7h Nevertheless, the developed methods are often restricted to the transfer of one type of acetylenes (either silyl-, aryl-or alkyl-substituted). Furthermore, 2-iodobenzoic acid is usually obtained as a stoichiometric byproduct after alkynylation, resulting in low atom economy. 8 Recently, Greaney and co-workers 9a and Dauban and co-workers 9b reported more atom economical transformations based on the use of the formed aryl iodides in cross-coupling reactions with aryliodonium salts and PhI(OPiv)2, respectively. With EBX reagents, progress in this area has been limited to a report of Yoshikai and coworkers on the palladium-catalyzed reaction of imines with alkynylbenziodoxolones to give furan derivatives. 10 Scheme 1. Alkynylation strategies and multi-component reactions usin...

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Section: Scheme 1 Alkynylation Strategies and Multi-component Reactimentioning

confidence: 99%

Copper-Catalyzed Oxy-Alkynylation of Diazo Compounds with Hypervalent Iodine Reagents

2016

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“…Ketene chemistry remains a very active area of research worldwide, involving both synthetic and mechanistic studies, and has been extensively reviewed. [3][4][5][6][7][8][9][10][11][12][13][14][15] This review describes the most recent work in the area, which is rich in further opportunities. The organization of this review includes separate headings on ketene preparation and on ketene reactions, but since ketenes are usually short-lived intermediates ketene formation and reactivity are usually inextricably mixed, and examples of one almost invariably contain the other.…”

Section: Introductionmentioning

confidence: 99%

Recent advances in ketene chemistry

Allen¹,

Tidwell²

2016

Arkivoc

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Recent advances in ketene chemistry are reviewed, including synthetic, mechanistic, and computational studies. Topics include ketene structure determination by experimental and theoretical methods, computational studies of bonding in ketenes, spectroscopic properties of ketenes, preparation and formation of ketenes including photochemical and thermal methods, the discovery and observation of ketenes in space, and ketene reactions. The last category includes decarbonylation, cycloadditions with carbon-carbon, carbon-nitrogen, and carbon-oxygen multiple bonds, addition of oxygen, nitrogen, and carbon nucleophiles, and electrophilic additions.

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“…Im Allgemeinen wird eine elektronenziehende Gruppe,h äufig eine Carbonylgruppe,b enç-tigt, um den Einbau der Diazogruppe zu ermçglichen und die Stabilitätd er resultierenden Diazomoleküle füre ine bessere Handhabung zu erhçhen. [154] Ein Rhodium(II)-Salz kann eingesetzt werden, um die Spaltung der Diazogruppe zu katalysieren. Das als Intermediat gebildete Rhodiumcarbenoid kann in eine Alkyl-C-H-Bindung insertieren, was zur Bildung einer C-C-Bindung führt.…”

Section: Carbentransferunclassified

Komplementäre Strategien für die dirigierte C(sp³)‐H‐Funktionalisierung: ein Vergleich von übergangsmetallkatalysierter Aktivierung, Wasserstoffatomtransfer und Carben‐ oder Nitrentransfer

2017

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Funktionalisierungen von C(sp3)‐H‐Bindungen verkürzen und vereinfachen chemische Synthesen, indem sie die Verwendung einfacher Moleküle ermöglichen und neuartige Retrosynthesen bereitstellen. Intensive Forschungen, die auf die Entwicklung neuer Reaktionen basierend auf dem Ansatz der C‐H‐Funktionalisierung abzielten, haben zur weiten Verbreitung dieser Methoden in einer Vielzahl von Bereichen geführt. Dieser Aufsatz erörtert die Stärken und Schwächen der drei Hauptstrategien – übergangsmetallkatalysierte C‐H‐Aktivierung, 1,n‐Wasserstoffatomtransfer und übergangsmetallkatalysierter Carben‐ oder Nitrentransfer – in der gezielten Funktionalisierung nichtaktivierter C(sp3)‐H‐Bindungen. Für jede Strategie werden der Anwendungsbereich, die Reaktivität verschiedener C‐H‐Bindungen, die Position der reagierenden C‐H‐Bindungen bezüglich der dirigierenden Gruppe und die stereochemischen Auswirkungen mit Beispielen aus der Literatur veranschaulicht. Das Ziel dieses Aufsatzes ist es, dem Anwender von C‐H‐Funktionalisierungsreaktionen eine Orientierungshilfe zu geben und künftige Forschungen auf diesem Gebiet anzuregen.

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Modern Organic Synthesis with α-Diazocarbonyl Compounds

Cited by 1,373 publications

References 838 publications

Copper-Catalyzed Oxy-Alkynylation of Diazo Compounds with Hypervalent Iodine Reagents

Copper-Catalyzed Oxy-Alkynylation of Diazo Compounds with Hypervalent Iodine Reagents

Recent advances in ketene chemistry

Komplementäre Strategien für die dirigierte C(sp³)‐H‐Funktionalisierung: ein Vergleich von übergangsmetallkatalysierter Aktivierung, Wasserstoffatomtransfer und Carben‐ oder Nitrentransfer

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Modern Organic Synthesis with α-Diazocarbonyl Compounds

Cited by 1,373 publications

References 838 publications

Copper-Catalyzed Oxy-Alkynylation of Diazo Compounds with Hypervalent Iodine Reagents

Copper-Catalyzed Oxy-Alkynylation of Diazo Compounds with Hypervalent Iodine Reagents

Recent advances in ketene chemistry

Komplementäre Strategien für die dirigierte C(sp3)‐H‐Funktionalisierung: ein Vergleich von übergangsmetallkatalysierter Aktivierung, Wasserstoffatomtransfer und Carben‐ oder Nitrentransfer

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Komplementäre Strategien für die dirigierte C(sp³)‐H‐Funktionalisierung: ein Vergleich von übergangsmetallkatalysierter Aktivierung, Wasserstoffatomtransfer und Carben‐ oder Nitrentransfer