Utilisation en synthese du cation iminium genere in situ par oxydation electrochimique d'amines tertiaires

Bidan, Gérard; Genies, M.

doi:10.1016/s0040-4020(01)97987-6

Cited by 28 publications

(9 citation statements)

References 23 publications

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“…[39] Later, the groups of Dinnocenzo, Fari, and Gould quantified Genies assumption and calculated a twist angle of 428 between the aryl ring and the dimethyl-A C H T U N G T R E N N U N G amino group in the radical cation 1lC…”

Section: A-phosphonationmentioning

confidence: 99%

Iron‐Catalyzed Oxidative Mono‐ and Bis‐Phosphonation of N,N‐Dialkylanilines

2010

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Abstract:The dehydrogenative a-phosphonation of substituted N,N-dialkylanilines by dialkyl H-phosphonates was achieved under mild conditions by using environmentally benign iron(II) chloride as catalyst and tert-butyl hydroperoxide as oxidant. The reaction proceeded in the presence of electron-donating (methoxy, methyl, benzyl) and electron-withdrawing ring-substitutents (bromo, carbonyl, carboxyl, m-nitro) in moderate to good yields. The X-ray crystal structure of N-(5,5-dimethyl-2-oxo-2l 5 -[1,3,2]dioxaphosphinan-2-yl-methyl)-N-methyl-p-toluidine was determined. Bis-(4-(dimethylamino)phenyl)methane and bis-4,4'-(dimethylamino)benzophenone underwent bisphosphonation selectively by respective monophosphonation at the remote dimethylamino groups. Furthermore, the use of excess di-

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Section: A-phosphonationmentioning

confidence: 99%

Iron‐Catalyzed Oxidative Mono‐ and Bis‐Phosphonation of N,N‐Dialkylanilines

2010

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“…This 6-effect of 4.9 ppm is comparable with the 6-effect of 5 ppm observed for 2-methyl cyclohexane (12). The carbonyl carbon appears at 214.68 ppm and 212.97 ppm for the axial and the 4~ complete study on the electrochemical oxidation of N,N-dimethylrneiidine in the presence of nucleophiles has been published (7,8).…”

Section: Resultsmentioning

confidence: 99%

“…Recently, it 3 was shown that the iminium cation, obtained from the electrochemical oxidation of N,N-dimethylanilines, gave good yields of addition products with nucleophiles such as diethyl phos-R ' 1 I phate and dialkylmalonates (7,8). It seemed to be interesting \N-CH~-C-C-R~ for us to study the preparation of Mannich bases 4 by the R2"…”

Section: // ' C=c \Rsmentioning

confidence: 99%

“…The electrochemical formation of iminium cations from tertiary amines has been extensively studied (6)(7)(8)(9). Recently, it 3 was shown that the iminium cation, obtained from the electrochemical oxidation of N,N-dimethylanilines, gave good yields of addition products with nucleophiles such as diethyl phos-R ' 1 I phate and dialkylmalonates (7,8).…”

Section: // ' C=c \Rsmentioning

confidence: 99%

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Synthesis of Mannich bases from electrochemically generated iminium salts in the presence of silyl enol ethers

Renaud¹,

Bérubé²,

Stephens³

1983

Can. J. Chem.

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. Can. J. Chem. 61, 1379 (1983). The formation of Mannich bases from the reaction of silyl enol ethers with N-methyl-N-mesitylmethylcniminium salt, generated by the electrochemical oxidation of N,N-dimethylmesidine, was studied. Important factors influencing the reaction are: (a) the silyl enol ether must be nucleophilic enough to react with the iminium salt and, at the same time, must be more difficult to oxidize than the tertiary amine, (b) the product of the reaction must not be oxidized at the operating potential. Examples are presented in this paper illustrating the successes and limitations of this reaction.ROGER N. RENAUD, DENIS BERUBE et CAMPBELL J . STEPHENS. Can. J . Chem. 61, 1379 (1983). La formation de bases de Mannich a @tk ktudiCe en faisant rkagir des ethers silyl Cnoliques sur le sel N-mCthyl-Nmksitylmtthyleniminium prtparC par oxydation Clectrochimique de la N,N-dimkthylmtsidine. Les facteurs pouvant influencer la rCaction sont: (a) l'ether silyl knolique doit Ctre assez nucltophilique pour rtagir avec le sel iminium et, en meme temps, doit Ctre plus difficile i oxyder que I'amine tertiaire, (b) Ic produit de la reaction ne doit Ctre oxydi: au potentiel employk. Des exemples montrant le succes et la limitation de cette rkaction sont prtsentks dans cette dtude. // ' C=C \RSThe electrochemical formation of iminium cations from tertiary amines has been extensively studied (6-9). Recently, it 3 was shown that the iminium cation, obtained from the electrochemical oxidation of N,N-dimethylanilines, gave good yields of addition products with nucleophiles such as diethyl phos-R ' 1 I phate and dialkylmalonates (7,8). It seemed to be interesting \N-CH~-C-C-R~ for us to study the preparation of Mannich bases 4 by the R2" Inucleophilic attack of silyl en01 ethers 3 on electrochemically prepared iminium cations 2, according to Scheme I . Only a 4 selection of silyl en01 ethers in the presence of the iminium salt SCHEME I of N,N-dimethylmesidine 1 are reported in this paper in order to present the scope of the potential of this preparative method.the products have to be considered. Figure 1 illustrates the Results and discussionControlled potential electrolyses were performed at a platinum electrode in acetonitrile containing 0.1 M lithium perchlorate. By using a one-compartment cell, a dark solution and an electrode passivation were obtained. The current was reversed for 2 s every minute in order to regenerate the surface of the electrode. A two-compartment cell eliminated these problems and simplified the purification of the products. Nevertheless, the yield of products increased only slightly by using a divided cell. Good yields (Table 1) of ~L I -4~i were obtained' for the electrolysis of N,N-dimethylmesidine in the presence of the silyl en01 ethers 3a-3ri, respectively. However, the Mannich base 4 e was obtained in low yield froni 3 e while 4f was not detected from 3f.Examination of the oxidation potentials of the reactants and the products gave some light on the electrolysis results. The current-pote...

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“…10 A different method to afford a-aminophosphonates especially from the tertiary amines is the cross-dehydrogenative-coupling (CDC) reaction between a sp 3 C-H bond adjacent to a nitrogen atom and a P-H bond. In 1981, Genies and co-workers 11 reported a CDC reaction of dialkyl phosphonates with tertiary amines through electrical oxidation albeit with moderate yields. In 2001, Tilley and co-workers 12 reported an intramolecular C-H/P-H dehydrogenative coupling catalyzed by Rh complex.…”

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confidence: 99%

Direct oxidative phosphonylation of amines under metal-free conditions

Wang

et al. 2012

Tetrahedron Letters

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Utilisation en synthese du cation iminium genere in situ par oxydation electrochimique d'amines tertiaires

Cited by 28 publications

References 23 publications

Iron‐Catalyzed Oxidative Mono‐ and Bis‐Phosphonation of N,N‐Dialkylanilines

Iron‐Catalyzed Oxidative Mono‐ and Bis‐Phosphonation of N,N‐Dialkylanilines

Synthesis of Mannich bases from electrochemically generated iminium salts in the presence of silyl enol ethers

Direct oxidative phosphonylation of amines under metal-free conditions

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