Synthesis of Heterocyclic Allenes via Palladium-Catalyzed Hydride-Transfer Reaction of Propargylic Amines

Nakamura, Hiroyuki; Onagi, Shinya; Kamakura, Takaya

doi:10.1021/jo0479664

Cited by 31 publications

(20 citation statements)

References 31 publications

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“…Therefore, it seemed possible that 6 were the precursors of the observed allenes 7, as postulated for the Crabbé homologation (19,20,39). Palladium has also been shown to fragment preformed propargylamines to yield allenes.…”

Section: Resultsmentioning

confidence: 98%

Allene formation by gold catalyzed cross-coupling of masked carbenes and vinylidenes

Lavallo

Frey

Kousar

et al. 2007

Proc. Natl. Acad. Sci. U.S.A.

282

165

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Section: Resultsmentioning

confidence: 98%

Allene formation by gold catalyzed cross-coupling of masked carbenes and vinylidenes

Lavallo

Frey

Kousar

et al. 2007

Proc. Natl. Acad. Sci. U.S.A.

282

165

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“…(14)) [18]. (14) Heterocyclic ring systems were shown to readily participate in Sonogashira-type couplings [175,306]. Some more complex examples include reaction of 5-iodoarabinosyluridine [307], 3-iodofuran [308], 6-chloro-9H-purine [309], 8-bromoadenosine [310], 2,6-bis(4-iodopyrazol-1-yl)pyridine [311], 6-chloro-3H-pyrimidin-4-one [312], bromo-oxabicyclo[3.2.1]octadienes [28], a triazolopyrazinyl bromide [172], 5-trifloxyindoles [29], 5-bromobenzofuran [183], 3-iodo-5-bromoindole and 3-iodo-5-bromo-3-indazole [182], 7-bromo-pyrido [2,3-b]pyrazine [185], 5-iodo-1,2,3-triazoles [186,313], 4,5-diiodoimidazole [314] and 4-iodo-2-bromoquinoline [315] derivatives.…”

Section: Carbon-carbon Bond-forming Reactions Using Terminal Alkynes mentioning

confidence: 99%

Transition metals in organic synthesis: Highlights for the year 2005

Söderberg

2008

Coordination Chemistry Reviews

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“…Moreover, steric factors can play an important role in these reactions. Nakamura et al performed straightforward Sonogashira couplings in solution with heteroaryl bromides and N,N-diisopropylpropargylamine [31]. Additionally, Santelli and co-workers obtained the best results with bulky, tertiary amines [30].…”

mentioning

confidence: 99%

The Sonogashira Coupling of Polymer‐Supported Propargylamine with Aryl Iodides

Leikoski¹,

Kallonen²,

Yli‐Kauhaluoma³

2010

Helvetica Chimica Acta

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The Sonogashira coupling reaction of polymer-supported propargylamine (¼ prop-2-yn-1-amine) with aryl iodides in the presence of the [Pd(PPh 3 ) 2 ]Cl 2 /CuI catalyst system produces 3-arylprop-1-yn-1-amines smoothly at room temperature (Scheme). When propargylamine is attached on Wang resin through a carbamate linker, the common problems with amino functionality in palladium-catalyzed couplings are overcome. The arylpropynamines are cleaved from the polymer with CF 3 COOH and converted into chromatographically easily separable acetamides. Our solid-phase method opens a new pathway toward precursors of pharmacologically interesting arylpropynamines and arylpropanamines.Introduction. -Aryl-and heteroarylpropanes are common precursors of biologically important natural products, e.g., of lignin [1] and lignans [2]. In addition, some 3-aryl-or 3-heteroarylpropan-1-amine derivatives have been associated with central nervous system stimulating [3], antimalarial [4], positive inotropic [5], and antifungal [6] properties. We embarked on the solid-phase Sonogashira coupling reactions of polymer-bound propargylamine (¼ prop-2-yn-1-amine) with various aryl iodides. The 3-arylpropargylamines obtained in this coupling reaction can be reduced into 3-arylpropan-1-amines of interest. On the other hand, substituted arylpropargylamines themselves are interesting compounds since some of them, or their metabolites, possess selective inhibitory activity toward physiologically significant enzymes, such as aldehyde dehydrogenase [7] and monoamine oxidase B [8].The Sonogashira coupling is an efficient palladium-catalyzed method for constructing aryl-and heteroarylacetylenes [9]. This reaction has been widely studied in liquid-phase synthesis, and due to its general efficiency, e.g., high yields, tolerance of a wide range of functional groups, and a simple one-step procedure, it has in most applications replaced the analogous reaction of copper acetylide, the Castro -Stephens reaction [10]. Although the Sonogashira coupling in solid-phase reactions has been studied to a lesser extent, there are substantial amount of reports, where the benefits of the use of polymer-supported reagents have been combined with the high performance of this reaction [11 -24]. On the other hand, both the aryl iodide and the acetylene components have been successfully used as polymer-bound reactants. For example, Moore and co-workers generated a resin-bound terminal acetylene by deprotecting the trimethylsilyl group with Bu 4 NF, and subjected it to Sonogashira conditions with (trimethylsilyl)acetylene-funtionalized aryl iodides [11]. After repeating the reaction cycles, oligomeric arylacetylenes were obtained as final products. Huang and Tour applied a related sequence-specific methodology in solid-phase synthesis of linear,

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Synthesis of Heterocyclic Allenes via Palladium-Catalyzed Hydride-Transfer Reaction of Propargylic Amines

Cited by 31 publications

References 31 publications

Allene formation by gold catalyzed cross-coupling of masked carbenes and vinylidenes

Allene formation by gold catalyzed cross-coupling of masked carbenes and vinylidenes

Transition metals in organic synthesis: Highlights for the year 2005

The Sonogashira Coupling of Polymer‐Supported Propargylamine with Aryl Iodides

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