Formation of Enamides via Palladium(II)-Catalyzed Vinyl Transfer from Vinyl Ethers to Nitrogen Nucleophiles

Brice, Jodie L.; Meerdink, James E.; Stahl, Shannon S.

doi:10.1021/ol0494360

Cited by 101 publications

(37 citation statements)

References 51 publications

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“…Systematic investigations revealed that a base, for example, potassium carbonate or hydroxide, is essential, whereas the alcohol can be replaced by water (entries [5][6][7][8][9]. This goes along with reports in the literature that phosphines themselves can act as reducing agents for transition metals, a process assisted by water.…”

mentioning

confidence: 99%

“…They promise to be valuable alternatives to traditional syntheses, for example, from carbonyl compounds and amides [6] or from hydroxylamines and carboxylic anhydrides, [7] that usually require harsh conditions and give (E/Z)-mixtures, and to metal-catalyzed coupling reactions of amides with vinyl halides, pseudohalides [8] or ethers, [9] which suffer from limited substrate availability.…”

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confidence: 99%

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A Practical and Effective Ruthenium Trichloride‐Based Protocol for the Regio‐ and Stereoselective Catalytic Hydroamidation of Terminal Alkynes

et al. 2008

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A rational catalyst development based on mechanistic and spectroscopic investigations led to the discovery of a new protocol for catalytic hydroamidation reactions that draws on easily available ruthenium trichloride trihydrate (RuCl 3 ·3 H 2 O) as the catalyst precursor instead of the previously employed, expensive bis(2-methylallyl)(1,5-cyclooctadiene)ruthenium(II). This practical and easy-to-use protocol dramatically improves the synthetic applicability of Ru-catalyzed hydroamidations. The catalyst, generated in situ from rutheniumA C H T U N G T R E N N U N G (III) chloride hydrate, tri-n-butylphosphine, 4-(dimethylamino)-pyridine and potassium carbonate, effectively promotes the addition of secondary amides, lactams and carbamates to terminal alkynes under formation of (E)-anti-Markovnikov enamides. The scope of the new protocol is demonstrated by the synthesis of 24 functionalized enamide derivatives, among them valuable intermediates for organic synthesis.

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confidence: 99%

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confidence: 99%

A Practical and Effective Ruthenium Trichloride‐Based Protocol for the Regio‐ and Stereoselective Catalytic Hydroamidation of Terminal Alkynes

et al. 2008

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“…Traditional syntheses-for example, from carbonyl compounds and amides [12] or from hydroxylamines and acetic anhydride [13] -require harsh conditions and yield mixtures of E/Z products. Metal-catalyzed coupling reactions of vinyl halides, [14] vinyl triflates, [15] or vinyl ethers [16] proceed under milder conditions but suffer from the limited availability of these substrates.…”

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confidence: 99%

Ru‐Catalyzed Anti‐Markovnikov Addition of Amides to Alkynes: A Regio‐ and Stereoselective Synthesis of Enamides

2005

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“…34 was transformed into 35 using the same method as in the case of 28. After for- 55) ring-closing metathesis was performed in the presence of 30, affording cyclic compound 37. Introduction of a hydroxyl group followed by oxidation of the resulting crude lactamol with PCC gave the known lactam (R)-(ϩ)-38.…”

Section: Asymmetric Allylic Alkylation Using Nitromethane As the Nuclmentioning

confidence: 99%

Transition Metal-Catalyzed Asymmetric Reactions Using P-Chirogenic Diaminophosphine Oxides: DIAPHOXs

Nemoto

2008

CHEMICAL & PHARMACEUTICAL BULLETIN

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This review describes the development of a new class of chiral phosphorus ligands: amino acid-derived Pchirogenic diaminophosphine oxides, DIAPHOXs, and their application to several transition metal-catalyzed asymmetric allylic substitution reactions. Pd-catalyzed asymmetric allylic alkylation with cyclic b b-keto esters as prochiral nucleophiles was initially examined using P-chirogenic diaminophosphine oxide 1a, resulting in highly enantioselective construction of quaternary stereocenters. Mechanistic investigations revealed that 1a is activated by N,O-bis(trimethylsilyl)acetamide-induced tautomerization to afford a trivalent diamidophosphite species 13, which functions as the actual ligand. Pd-catalyzed asymmetric allylic substitutions of both acyclic and cyclic substrates were also examined using various nucleophiles such as malonate derivatives, nitromethane, aliphatic amines, and aromatic amines, providing a variety of chiral compounds with good to excellent enantioselectivity. In addition, Ir-catalyzed asymmetric allylic amination and alkylation of terminal allylic carbonates were examined using structurally optimized P-chirogenic diaminophosphine oxides, and the corresponding branched products were obtained in a highly regio-and enantioselective manner. Furthermore, the developed catalytic asymmetric process was successfully applied to the catalytic enantioselective synthesis of biologically active compounds, (R)-preclamol, (R)-baclofen hydrochloride, and (؊)-paroxetine.

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Formation of Enamides via Palladium(II)-Catalyzed Vinyl Transfer from Vinyl Ethers to Nitrogen Nucleophiles

Cited by 101 publications

References 51 publications

A Practical and Effective Ruthenium Trichloride‐Based Protocol for the Regio‐ and Stereoselective Catalytic Hydroamidation of Terminal Alkynes

A Practical and Effective Ruthenium Trichloride‐Based Protocol for the Regio‐ and Stereoselective Catalytic Hydroamidation of Terminal Alkynes

Ru‐Catalyzed Anti‐Markovnikov Addition of Amides to Alkynes: A Regio‐ and Stereoselective Synthesis of Enamides

Transition Metal-Catalyzed Asymmetric Reactions Using P-Chirogenic Diaminophosphine Oxides: DIAPHOXs

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