Catalytic Decarboxylative Alkenylation of Enolates

Schröder, Sybrin P.; Taylor, Nicholas J.; Jackson, P. M.; Franckevičius, Vilius

doi:10.1021/ol401729m

Cited by 34 publications

(35 citation statements)

References 36 publications

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“…The resulting solid was dissolved in EtOAc and purified by column chromatography (hexane/EtOAc, 1:2) to afford 12 (3.6 g, 83 %) as a white solid. The spectroscopic data of 12 were identical to those of the previous report …”

Section: Methodssupporting

confidence: 82%

“…Our synthetic study started by preparing diketone 10 from dimedone ( 11 ) as shown in Scheme . Mono‐methylation to the activated methylene moiety of dimedone ( 11 ) by using a modified procedure reported by Franckevicius gave compound 12 in 83 % yield. Although the direct introduction of the butenyl group to compound 12 was attempted under several conditions, desired diketone 10 was obtained in low yield.…”

Section: Resultsmentioning

confidence: 99%

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Diastereoselective Total Synthesis of (±)‐Toxicodenane A

et al. 2017

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The first total synthesis of tricyclic sesquiterpene (±)‐toxicodenane A has been accomplished. This synthetic work was completed in 12 steps from dimedone through diastereoselective reductive desymmetrization of 2,2‐disubstituted 5,5‐dimethylcyclohexane‐1,3‐dione, stereocontrolled allylation, ring‐closing metathesis of a diene compound to yield bicyclic compounds that bear a seven‐membered ring, and construction of the oxygen‐bridged moiety through neighboring group assisted ring‐opening reaction of an epoxide as key steps.

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Section: Methodssupporting

confidence: 82%

Section: Resultsmentioning

confidence: 99%

Diastereoselective Total Synthesis of (±)‐Toxicodenane A

et al. 2017

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“…We reasoned that, if the  3 - This strategy proved to be successful in the coupling of propargyl enol carbonates 132 with phenols 74 to give 135, which contains an all-carbon quaternary center (Scheme 30). 41 A variety of cyclic and acyclic 1,3-dicarbonyls, as well as phenols decorated with electron-donating, -withdrawing and nucleophilic groups can be readily used, affording products 135a-g in high yields with complete chemo-and regioselectivity. Mechanistic studies indicated that the palladium center was indeed tightly associated with the enolate after decarboxylation, resulting in complete control of selectivity.…”

Section: Control Of Selectivity: Intermolecular Coupling Reactions Ofmentioning

confidence: 99%

Palladium-catalyzed construction of quaternary carbon centers with propargylic electrophiles

Franckevičius

2016

Tetrahedron Letters

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This short review describes the broad reactivity of propargylic electrophiles with nucleophiles under palladium catalysis for the construction of quaternary carbon centers, leading to allenylation, propargylation and alkenylation / allylic alkylation. Although the allenylation and propargylation of a nucleophile can readily create congested carbon centers, these processes often compete and require careful tuning of substrate structure and reactivity of the nucleophile. The alkenylation / allylic alkylation sequence is a much more studied reactivity mode, which results in the coupling of two nucleophiles. This approach is very popular for the rapid generation of molecular complexity, but also poses several chemo-and regioselectivity issues. These selectivity problems have been traditionally overcome by tethering strategies and cyclization reactions. However, over the past few years, highly selective intermolecular coupling reactions of nucleophiles have also been developed. It is, therefore, unsurprising that, as our prowess to control selectivity has grown, the first methods for the palladium-catalyzed enantioselective installation of quaternary carbon centers with propargylic electrophiles have also appeared.

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“…Indeed, we have found this to be the case in the coupling of 1,3-dicarbonyls with phenols to generate structures of type 12. 13 Subsequently, we reported the coupling of two different 1,3-dicarbonyl compounds (13), 14 the regioselectivity of which can be controlled by judiciously adding one of the nucleophiles as the propargyl enol carbonate. In the first instance, we tested the reactivity of propargylic carbonate 15a derived from a 1,3diketone and indole (16a) in the presence of a source of palladium(0) and a phosphine ligand in 1,4dioxane as the solvent at 80 °C (Table 1).…”

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confidence: 99%

“…H and13 C NMR spectra for all novel compounds.Mass and 1 H NMR spectra of compounds arising from deuterium-labeling experiments.Crystallographic data for 17d and 23b (CIF).…”

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confidence: 99%

Catalytic Chemo- and Regioselective Coupling of 1,3-Dicarbonyls with N-Heterocyclic Nucleophiles

2016

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The development of a decarboxylative palladium-catalyzed coupling of 1,3-dicarbonyl compounds with indole, pyrrole, imidazole, and pyrazole nucleophiles via an allylic linker under neutral conditions is disclosed. This process enables the installation of an all-carbon quaternary center and new C-C and C-N bonds in a single operation. Despite the weakly acidic nature of N-heterocycles, the reactions proceed with good efficiency and complete regio- and chemoselectivity.

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Catalytic Decarboxylative Alkenylation of Enolates

Cited by 34 publications

References 36 publications

Diastereoselective Total Synthesis of (±)‐Toxicodenane A

Diastereoselective Total Synthesis of (±)‐Toxicodenane A

Palladium-catalyzed construction of quaternary carbon centers with propargylic electrophiles

Catalytic Chemo- and Regioselective Coupling of 1,3-Dicarbonyls with N-Heterocyclic Nucleophiles

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