First evidence for the use of polyamines as nucleophiles in a regioselective palladium-catalyzed allylic amination reaction

Pieri, Cyril; Combes, Sébastien; Brunel, Jean Michel

doi:10.1016/j.tet.2014.10.019

Cited by 5 publications

(7 citation statements)

References 25 publications

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“…To explore the possibility of converting neral ( 2 ) to geranial ( 1 ) under the reaction conditions, we have incubated aldehyde 2 , produced by nerol ( 6 ) oxidation by MnO 2 , in the presence of K10 . We have found that neral ( 2 ) completely converts to cyclization and oligomerization products as early as after 15 min, with no geranial ( 1 ) being present in the reaction mixture.…”

Section: Resultsmentioning

confidence: 99%

“…Citral (ABCR, Karlsruhe, Germany) ((E/Z) = 1:1, 1 H-NMR); purity 96%. Neral (2) was synthesized from nerol (6) (Acros, Geel, Belgium) according to previously described methods [7]. Montmorillonite K10 (Aldrich, St. Louis, Missouri, USA) was calcined at 105°C for 3 h before the reaction.…”

Section: Generalmentioning

confidence: 99%

“…(2S,4R,4aR,8aS)-2-[(1E)-2,6-Dimethylhepta-1,5-dien-1-yl]-3,4,4a,5,6,8a-hexahydro-4,7-dimethyl-2H-1-benzopyran-4ol (7). ½a 20 580 = 0 (c = 3, CHCl 3 ).…”

Section: Isolation Of Geranial 1 From Citralmentioning

confidence: 99%

“…Geranial ( 1 ) was isolated from citral by high‐performance liquid chromatography . The most common laboratory method for production of geranial ( 1 ) is the selective oxidation of geraniol ( 3 ) using different systems, such as MnO 2 , the Dess – Martin reagent , [bis(acetoxy)iodo]‐benzene , oxygen in the presence of catalysts containing noble metals (Pd, Pt, Au, Ru, and Rh) , or the Swern , Corey – Kim , and Oppenauer oxidation reactions . The disadvantages of the existing methods of obtaining individual citral isomers by oxidation of the appropriate alcohols include high cost reagents, stringent requirements for the reaction conditions, difficulties in handling of reaction mixtures and catalysts regeneration, and the need of special equipment.…”

Section: Introductionmentioning

confidence: 99%

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The Convenient Way for Obtaining Geranial by Acid‐Catalyzed Kinetic Resolution of Citral

Ильина

Волчо

Корчагина

et al. 2016

Helvetica Chimica Acta

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A new simple method has been developed for isolation of geranial from citral, which is a mixture of two isomeric aldehydes, geranial and neral. The storage of citral in the presence of K10 montmorillonite clay has been demonstrated to result in an almost complete conversion of neral to dimeric and oligomeric products, with most geranial remaining unconverted. This enables isolation of geranial with the yield of up to 94%, based on the amount of geranial originally present in citral.

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Section: Resultsmentioning

confidence: 99%

Section: Generalmentioning

confidence: 99%

“…(2S,4R,4aR,8aS)-2-[(1E)-2,6-Dimethylhepta-1,5-dien-1-yl]-3,4,4a,5,6,8a-hexahydro-4,7-dimethyl-2H-1-benzopyran-4ol (7). ½a 20 580 = 0 (c = 3, CHCl 3 ).…”

Section: Isolation Of Geranial 1 From Citralmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

The Convenient Way for Obtaining Geranial by Acid‐Catalyzed Kinetic Resolution of Citral

Ильина

Волчо

Корчагина

et al. 2016

Helvetica Chimica Acta

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“…A large number of experimental and theoretical studies have been conducted to supplement the information concerning the influence of solvents on chemical and biological reactions . As reaction media, solvents can generally affect yields of reactions or even change reaction mechanisms . Furthermore, satisfactory results can also be obtained when solvents participate directly in reactions .…”

Section: Introductionmentioning

confidence: 99%

Mechanistic Insights into the Cu(I)- and Cu(II)-Catalyzed Cyclization of o-Alkynylbenzaldehydes: The Solvent DMF and Oxidation State of Copper Affect the Reaction Mechanism

Yuan

Shen

et al. 2015

J. Org. Chem.

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A computational study with the BhandHLYP density functional is conducted to elucidate the mechanisms of Cu(I)- and Cu(II)-catalyzed reactions of o-alkynylbenzaldehydes with a nucleophile (MeOH). Our calculations suggest the following. (a) The use of CuCl as a catalyst deceases significantly the energy barrier and promotes intramolecular cyclization. (b) Solvent DMF is critical in the stepwise hydrogen-transport process involved in an intermolecular nucleophilic addition because it can greatly reduce the free energy barrier of the hydrogen-transfer process as a proton shuttle. In addition, we find that substrate MeOH also plays a role similar to that of DMF in the hydrogen-transport reaction. (c) The 6-endo product P1 is formed exclusively using a catalytic system consisting of CuCl and DMF, whereas a mixture of 6-endo product P1 and 5-exo product P2 in a ratio of ∼1:1 is produced using CuCl2 and DMF as a catalytic system. Our theoretical calculations reproduce the experimental results very well. This study is expected to improve our understanding of Cu(I)- and Cu(II)-catalyzed reactions involving Lewis base solvents and to provide guidance for the future design of new catalysts and new reactions.

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Design and synthesis of new polyamine quinoline antibiotic enhancers to fight resistant gram-negative P. aeruginosa bacteria

Troia

Siad

Giorgio

et al. 2022

European Journal of Medicinal Chemistry Reports

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First evidence for the use of polyamines as nucleophiles in a regioselective palladium-catalyzed allylic amination reaction

Cited by 5 publications

References 25 publications

The Convenient Way for Obtaining Geranial by Acid‐Catalyzed Kinetic Resolution of Citral

The Convenient Way for Obtaining Geranial by Acid‐Catalyzed Kinetic Resolution of Citral

Mechanistic Insights into the Cu(I)- and Cu(II)-Catalyzed Cyclization of o-Alkynylbenzaldehydes: The Solvent DMF and Oxidation State of Copper Affect the Reaction Mechanism

Design and synthesis of new polyamine quinoline antibiotic enhancers to fight resistant gram-negative P. aeruginosa bacteria

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