Synthesis of (spiro)cyclopentapyridinones via Csp3–H functionalization: a post-Ugi gold-catalyzed regioselective tandem cyclization

Vachhani, Dipak D.; Galli, Marzia; Jacobs, Jeroen; Meervelt, Luc Van; Eycken, Erik V. Van der

doi:10.1039/c3cc43418d

Cited by 96 publications

(33 citation statements)

References 48 publications

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“…63aed,f Van der Eycken utilized this methodology to synthesize cyclopentapyridinones, 64 while Ohno reported the synthesis of bi-and tricyclic pyrroles from N-propargyl ynamides under similar conditions. 65 Hashmi also reported the synthesis of benzothiophenes and benzofurans using similar chemistry, albeit via a different mechanism.…”

Section: Metal Vinylidenesmentioning

confidence: 99%

Recent advances in alkylidene carbene chemistry

Grainger

Munro

2015

Tetrahedron

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Section: Metal Vinylidenesmentioning

confidence: 99%

Recent advances in alkylidene carbene chemistry

Grainger

Munro

2015

Tetrahedron

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“…4 In addition to these cyclizations of 1,5-diynes, a recent study reports the cyclization of the 1,6-diyne product of a Ugi four-component reaction by dual gold catalysis. 5 The mechanistic insights gained from these reactions quickly led to the preparation of a pre-catalyst, TDAC (Traceless Dual Activation Catalyst), which delivers the necessary two gold moieties in the needed σ-and π-coordinated fashion (Scheme 2). 6 A similar binding picture has been found for both mixed coinage metal σ,π-complexes and for dicopper complexes.…”

Section: Introductionmentioning

confidence: 99%

Dual Gold Catalysis: Stepwise Catalyst Transfer via Dinuclear Clusters

2015

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The interest in and use of dual gold catalysts is forever increasing, but little is known of the mechanism for the catalyst transfer and its effect on the continued high turnover frequency. Herein, we present a computational investigation of the mechanism for the final intermolecular catalyst transfer in the synthesis of dibenzopentalene from 1-ethynyl-2-(phenylethynyl)benzene. Three different scenarios have been explored: a single catalyst transfer from the monoaurated product complex, the analogous water mediated single transfer, and a dual catalyst transfer from the diaurated product complex. Transition structures have been found for each step of the three possible pathways, and a stepwise dual catalyst transfer has proven to be the lowest energy pathway. We here describe a three-step transfer of two gold moieties from one dibenzopentalene to one diyne. This process directly gives the σ,π-gold coordinated diyne for the further intramolecular cyclization reaction.

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“…[7] In 2012, Zhang's group [8] and our group [9] independently described a new reactivity pattern of gold catalysts, in which two gold centres synchronously activate a diyne system (dual activation). [10] Herein, one gold center acts as p Lewis acidic compound activating one of the alkynes, whereas the other gold center forms a gold-acetylide, which then reacts as a nucleophile through the C a or C b atom (Scheme 2). Initially, the 5-endo cyclization pathway via the C b atom of the gold-acetylide was experimentally observed generating a gold-vinylidene species, which undergoes CÀH activation of nonactivated aliphatic [8, 9b] and aromatic [9a,c] CÀH bonds, as well as intermolecular CÀH bond activation processes (Scheme 2 a).…”

Section: Introductionmentioning

confidence: 99%

Gold‐Catalyzed Cyclization of Diynes: Controlling the Mode of 5‐endo versus 6‐endo Cyclization—An Experimental and Theoretical Study by Utilizing Diethynylthiophenes

Hansmann

Tšupova

Rudolph

et al. 2014

Chemistry A European J

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Herein, a dual-gold catalyzed cyclization of 3,4-diethynylthiophenes generating pentaleno[c]thiophenes through gold-vinylidenes and CÀH bond activation is disclosed. Various new heteroaromatic compounds-substrate classes unexplored to date-exhibiting three five-membered annulated ring systems could be synthesized in moderate to high yields. By comparison of the solid-state structures of the corresponding gold-acetylides, it could be demonstrated that the cyclization mode (5-endo versus 6-endo) is controlled by the electronic and not steric nature of the diyne backbone. Depending on different backbones, we calculated thermodynamic stabilities and full potential-energy surfaces giving insight into the crucial dual-activation cyclization step. In the case of the 3,4-thiophene backbone, in which the initial cyclization is rate and selectivity determining, two energetically distinct transition states could be localized explaining the observed 5-endo cyclization mode by classical transition-state theory. In the case of vinyl and 2,3-thiophene backbones, the theoretical analysis of the cyclization mode in the bifurcated cyclization area demonstrated that classical transition-state theory is no longer valid to explain the high experimentally observed selectivity. Herein, for the first time, the influence of the backbone and the aromatic stabilization effect of the 6-endo product in the crucial cyclization step could be visualized and quantified by calculating and comparing the full potential-energy surfaces.

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Synthesis of (spiro)cyclopentapyridinones via Csp3–H functionalization: a post-Ugi gold-catalyzed regioselective tandem cyclization

Abstract: A gold-catalyzed regioselective tandem cyclization of N-propynylbutynamide via Csp(3)-H functionalization has been described, providing a distinctive methodology for the architecture of cyclopentapyridinones as well as spirocyclopentapyridinones.

Cited by 96 publications

References 48 publications

Recent advances in alkylidene carbene chemistry

Recent advances in alkylidene carbene chemistry

Dual Gold Catalysis: Stepwise Catalyst Transfer via Dinuclear Clusters

Gold‐Catalyzed Cyclization of Diynes: Controlling the Mode of 5‐endo versus 6‐endo Cyclization—An Experimental and Theoretical Study by Utilizing Diethynylthiophenes

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