Decarbonylative Cycloaddition of Phthalic Anhydrides with Allenes

Ochi, Yosuke; Kurahashi, Takuya; Matsubara, Seijiro

doi:10.1021/ol200044y

Cited by 51 publications

(25 citation statements)

References 56 publications

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“…In accordance with previous observations, [3][4][5]17] an allene with an aromatic substituent gave a lower yield (4 be). Monosubstituted allenes bearing hydroxy (4 bb), ester (4 ac), and silyl ether (4 ad) functional groups can be smoothly transformed into the desired products.…”

Section: Honggen Wang and Frank Glorius*supporting

confidence: 92%

“…Intriguingly, the regioselectivity of the C À N bond-formation step (Scheme 1, type B) was in sharp contrast with that observed in other preactivation strategies (Scheme 1, type A), [3][4][5]17] wherein the nucleophilic attack or reductive elimination predominantely occurred at the more substituted end of the p-allyl metal intermediate. This unique feature might arise from the steric hindrance of the Cp* ligand, and the complete reversal of the selectivity may also benefit from the rather mild conditions of this reaction.…”

Section: Honggen Wang and Frank Glorius*mentioning

confidence: 78%

“…Intramolecular versions of this reaction lead to interesting carbo-or heterocyclic skeletons, frequently found in pharmaceuticals and materials. Alternatively, methods involving the denitrogenative or decarbonylative coupling of either triazoles [4] or phthalimides [5] with allenes have also been reported, although the limited availability of the precursor is a major concern (Scheme 2 b). [3] However, this method necessitates the use of halogenated starting materials, which require extra synthetic operations thus limiting their availability.…”

Section: Honggen Wang and Frank Glorius*mentioning

confidence: 99%

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Mild Rhodium(III)‐Catalyzed CH Activation and Intermolecular Annulation with Allenes

2012

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Section: Honggen Wang and Frank Glorius*supporting

confidence: 92%

Section: Honggen Wang and Frank Glorius*mentioning

confidence: 78%

Section: Honggen Wang and Frank Glorius*mentioning

confidence: 99%

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Mild Rhodium(III)‐Catalyzed CH Activation and Intermolecular Annulation with Allenes

2012

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“…Z-configuration of the exocyclic double bonds were established using NOE data (see the Experimental Section) and in the absence of ammonium tartrate, no reaction occurred, and only starting materials were observed. This appears to be consistent with a mechanism involving the addition of ammonia 70 to the -allyl intermediate forming amine 3 which subsequently cyclises to give 4. Thus, the cyclisation step in 3 4 is faster than further allylation of the allyl-NH 2 group.…”

supporting

confidence: 77%

A facile palladium catalysed 3-component cascade route to functionalised isoquinolinones and isoquinolines

et al. 2016

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Palladium catalysed three component cascade process, involving coupling of 2-iodobenzoates, -benzaldehydes, or acetophenones with substituted allenes and ammonium 10 tartrate as an ammonium surrogate, provides a novel and facile route to substituted functionalised isoquinolinones and isoquinolines in good yields.Isoquinolinone and isoquinoline derivatives are important 15 constituents of a diverse range of molecules of biological and pharmaceutical relevance as well as a common structural component within many alkaloids. 1,2,3 However, little attention has been given to approaches to these systems which utilise metal-catalysed aryl-allene couplings, despite the obvious 20 potential of this route to produce such systems with high degrees of chemo-and regioselectivity. Nonetheless, the potential of this approach has been underlined previously. Thus, Larock reported that annulation of a substituted allene with N-tosyl-2-iodobenzylamine under Pd(II) catalysis afforded isoquinolines as 25 a mixture of three regio-and stereo-isomers. 4 Additionally, 2-iodobenzaldehyde imines have also been used with Pd(0) catalysis to annulate substituted allenes giving isoquinoline derivatives. 5 Ni(0)/chiral phosphine ligand mediated regio-and enantioselective synthesis of isoquinoline-1(2H)-one derivatives 30 has been reported via denitrogenation or decarbonylation of Naryl-1,2,3-benzotriazin-4(3H)-ones or N-substituted phthalimide, respectively, followed by intermolecular annulation with substituted allenes. 6 Recently, Glorius et al., employed Rh(III) to catalyse C-H activation of N-(pivaloyloxy)benzamide involving 35 intermolecular annulation with substituted allenes to furnish isoquinoline-1(2H)-ones. 7 As part of our program of research into the development and application of palladium catalysed allene insertion cascades, we have previously reported a number of examples of three-40 component cascades for the synthesis of N-substituted 4-methylene-3,4-dihydro-1(2H)-isoquinolinones. A feature of these reactions is that, following an initial Pd-mediated intramolecular allene insertion, both intra-and intermolecular nucleophilic addition then occurs to give tetra-fused ring systems containing 45 an isoquinolinone ring. 8, 9a These include, following the initial Pd catalysed intramolecular allene insertion, intermolecular nucleophilic addition involving N-allenyl-2-iodobenzamide, 9b,c and nitrogen-tethered 1,6-enynes 9d respectively. Additionally, we have also reported two types of cascade reactions that can furnish 50 isoquinolines; (i) intermolecular allene insertion into the C-I bond of an aryl iodide linked N-nucleophile followed by intramolecular N-addition to the generated -allyl, 10 and (ii) intermolecular allene insertion to an aryl iodide carrying a dipolarophile/Michael acceptor followed by intermolecular N-addition of an azide/amine 55 and finally intramolecular 1,3-dipolar cycloaddition/Michael addition. 11 In the present study, we report a new approach utilising our "ammonium surrogate" technology 12 as a nove...

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“…[3] Jedoch erfordert diese Methode den Einsatz von halogenierten Reaktanten, die oft in einem zusätzlichen Syntheseschritt hergestellt werden müssen. Alternativ wurde über Methoden berichtet, welche eine Kupplung von Allenen mit Triazolen [4] unter Stickstoffabspaltung oder eine decarbonylierende Kupplung mit Phthalimiden [5] beinhalten. In diesem Fall ist jedoch die begrenzte Verfügbarkeit der Vorstufen ein großer Nachteil (Schema 2 b).…”

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Milde Rhodium(III)‐katalysierte C‐H‐Aktivierung und intermolekulare Anellierung mit Allenen

Wang¹,

Glorius²

2012

Angewandte Chemie

112

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Alle(ne) großartig! Eine neue RhIII‐katalysierte oxidative Kupplung mit Allenen unter milden Bedingungen liefert Heterocyclen mit exocyclischen Doppelbindungen. Diese Reaktion benötigt nur geringe Katalysatormengen und bietet eine hohe Regio‐ und Stereoselektivität sowie eine exzellente Substratbreite. Es wurden eine Derivatisierung der Produkte sowie erste mechanistische Studien durchgeführt.

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Decarbonylative Cycloaddition of Phthalic Anhydrides with Allenes

Abstract: The decarbonylative cycloadditions of phthalic anhydrides with allenes were performed by using nickel catalyst. The asymmetric variant of the cycloaddition was also achieved by using chiral phosphine ligands to provide δ-lactones enantioselectively.

Cited by 51 publications

References 56 publications

Mild Rhodium(III)‐Catalyzed CH Activation and Intermolecular Annulation with Allenes

Mild Rhodium(III)‐Catalyzed CH Activation and Intermolecular Annulation with Allenes

A facile palladium catalysed 3-component cascade route to functionalised isoquinolinones and isoquinolines

Milde Rhodium(III)‐katalysierte C‐H‐Aktivierung und intermolekulare Anellierung mit Allenen

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