Indium triflate catalyzed reaction of diisopropyl diazomethylphosphonate with imines as a new approach to cis- and trans-aziridine-2-phosphonates

Pellicciari, Roberto; Amori, Laura; Kuznetsova, Natalia; Zlotsky, S. S.; Gioiello, Antimo

doi:10.1016/j.tetlet.2007.05.042

Cited by 25 publications

(13 citation statements)

References 38 publications

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“…It was found that the reactions gave lower yields of the desired product in solvents such as CH 2 Cl 2 , H 2 O, CH 3 NO 2 after prolonged reaction time. (15)(16)(17)(18)(20)(21)(22)(23). We also checked the reusability of the catalyst by separation and reloading in a new run and found that the catalyst could be reused three times without any decrease in the yield (Entry 19).…”

Section: Resultsmentioning

confidence: 99%

“…In accordance with the recent surge of interest in indium(III) salts has emerged as a promising catalyst for various types of organic transformations. Particularly, indium tribromide, 18 indium trichloride 19 and indium trifluoromethanesulfonate 20 as a novel type of water-tolerant green Lewis acid catalyst have received considerable attention for various transformations, because they have advantages of water stability, operational simplicity, recyclability, strong tolerance to oxygen and nitrogencontaining reaction substrates and functional groups, and it can often be used in just catalytic amounts. Recently, Zhang 21 In continuation of our interest in Lewis acid-catalyzed and green chemistry organic reactions, 23 we herein wish to report a simple, practical and efficient method for the synthesis of pyrroles from -diketones and amines using indium(III) salt as catalyst at room temperature under solvent-free conditions (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

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Indium(III)-catalyzed synthesis of N-substituted pyrroles under solvent-free conditions

Chen¹,

Liu²,

Yang³

et al. 2008

J. Braz. Chem. Soc.

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Vários pirróis N-substituídos foram sintetizados pela reação de -dicetonas (R 1 C(O) CH 2 CH 2 C(O)R 2 : R 1 , R 2 = Me, Ph) com aminas (RNH 2 : R = Alkyl, Aryl, TsNH) ou diaminas (1,6-diaminohexano and 1,2-diaminoetano) na presença de tribrometo de índio, tricloreto de índio ou trifluorometanossulfonato de índio a temperatura ambiente e sem solventes. O protocolo envolve operações simples e os produtos são isolados em excelentes rendimentos (81-98%).A variety of N-substituted pyrroles have been synthesized by reacting -diketones (R 1 C(O) CH 2 CH 2 C(O)R 2 : R 1 , R 2 = Me, Ph) with amines (RNH 2 : R=Alkyl, Aryl, TsNH) or diamines (1,6-diaminohexane and 1,2-diaminoethane) in the presence of indium tribromide, indium trichloride or indium trifluoromethanesulfonate at room temperature under solvent-free conditions. The experiment protocol features simple operations, and the products are isolated in high to excellent yields (81-98%). Keywords: indium tribromide, indium trichloride, indium trifluoromethanesulfonate, pyrroles, solvent-free conditions IntroductionHeterocyclic small molecules play an important role in the search for new therapeutic and drug candidates. 1Pyrroles are an important class of heterocyclic compounds and are structural units found in a vast array of natural products, synthetic materials, and bioactive molecules, such as heme, vitamin B12, and cytochromes.2 Pyrroles also play crucial roles in nonlinear optical materials as well as in supramolecular chemistry.3 Therefore, the enormous number of procedures have been developed for the construction of pyrroles. Classical methods for their preparation include the Knorr, 4 Hantzsch, 5 and PaalKnorr condensation reactions. [6][7][8][9][10][11][12][13][14][15][16] Among these methods, the most commonly used and straightforward approach for the preparation of pyrroles is the direct condensation of -diketones and amines (Paal-Knorr reaction) in the presence of protonic acids such as AcOH, 6 p-TsOH. In continuation of our interest in Lewis acid-catalyzed and green chemistry organic reactions, 23 we herein wish to report a simple, practical and efficient method for the synthesis of pyrroles from -diketones and amines using indium(III) salt as catalyst at room temperature under solvent-free conditions (Scheme 1). Results and DiscussionInitially, the efficacy of various catalysts was tested in the model reaction under solvent-free condition at room temperature (Table 1). The results showed that InCl 3 , InBr 3 and In(OTf) 3 were superior to other Lewis acids with respect to reaction times and product yields. Entry 1 showed the blank reaction without addition of any catalyst, in this case only 29% 2,5-dimethyl-1-phenyl-1H-pyrrole (3a) was obtained after 24 h. For the sake of comparison, the reaction was carried out using other anhydrous chloride, such as ZnCl 2 , NiCl 2 , SrCl 2 and CuCl 2 under solvent free conditions (Entries 2-8). However, these chlorides showed lower activity than InCl 3 under same reaction conditions. We examined influence of solvents ...

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Indium(III)-catalyzed synthesis of N-substituted pyrroles under solvent-free conditions

Chen¹,

Liu²,

Yang³

et al. 2008

J. Braz. Chem. Soc.

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“…(3S,3aR,4R,7S,7aS)-3-Acetyl-hexahydro-7-isopropyl-4-methylbenzofuran-2(3H)-one (10). IR (KBr, cm -1 ): 1755 (s), 1725 (s), 1458 (m), 1385 (m), 1362 (m), 1289 (m), 1238 (m), 1154 (w), 992 (w); 1 H NMR (CDCl 3 , 400 MHz) d 3.72 (t, J = 7.2 Hz, 1H), 3.45 (d, J = 12.0 Hz, 1H), 2.42 (s, 3H), 2.37-2.27 (m, 1H), 1.96-1.92 (m, 1H), 1.78 (d, J = 9.6 Hz, 2H), 1.69 (t, J = 10.8 Hz, 1H), 1.47 (t, J = 5.6 Hz, 1H), 1.21-1.12 (m, 2H), 0.95 (d, J = 6.8 Hz, 3H), 0.9 (d, J = 7.2 Hz, 3H), 0.83 (d, J = 7.2 Hz, 3H); 13 C NMR (CDCl 3 , 100 MHz) d 202.…”

Section: Tetrahydromentioning

confidence: 99%

“…The corresponding aziridinecarboxylates are prepared generally in good yields. In addition to diazoacetates, other diazo compounds such as TMSCHN 2 , 9 diazophosphonates, 10 phenyldiazoactetates and styryldiazoacetates 11 were also successfully applied. On the other hand, addition of diazoacetoacetates to imines is also an attractive research subject and the reaction provides highly functionalized aziridines.…”

Section: Introductionmentioning

confidence: 99%

Catalyzed addition of diazoacetoacetates to imines: synthesis of highly functionalized aziridines

2009

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The addition of diazoacetoacetates to aromatic imines derived from p-methoxyaniline is achieved using dirhodium tetraacetate as the catalyst. Highly functionalized aziridines are obtained in good yield and with excellent stereoselectivity. 2-Diazo-1,3-diketones also provide good yields of aziridines, but dimethyl diazomalonate is inactive in the transformation. The diazoacetoacetates of chiral alcohols are also examined in the reaction and moderate diastereoselectivity is achieved with (R)-pantolactone-derived diazoacetoacetate. A reaction mechanism through metal-carbene and azomethine ylide is proposed.

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“…16 The development of procedures leading to the stereocontrolled formation of carbon-nitrogen bond is considered a challenging research target. Numerous methods are available for differently substituted aziridines, which include aziridination of olefins [17][18][19] (Scheme 1, route I), carbene and ylide addition to imines [20][21][22] (Scheme 1, route II), cyclization of b-amino alcohols, 23,24 b-amino halides, 23,24 b-azido alcohols 23-25 (Scheme 1, route III) and halo imines 26 (Scheme 1, route IV). However, only a few routes for the synthesis of C-nitroaziridines are available in the literature.…”

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confidence: 99%

The first diastereoselective nitroaziridination of N-tosylaldimines with 1-bromonitroalkanes

Yadav

Garima

Kapoor

2009

Tetrahedron Letters

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Indium triflate catalyzed reaction of diisopropyl diazomethylphosphonate with imines as a new approach to cis- and trans-aziridine-2-phosphonates

Cited by 25 publications

References 38 publications

Indium(III)-catalyzed synthesis of N-substituted pyrroles under solvent-free conditions

Indium(III)-catalyzed synthesis of N-substituted pyrroles under solvent-free conditions

Catalyzed addition of diazoacetoacetates to imines: synthesis of highly functionalized aziridines

The first diastereoselective nitroaziridination of N-tosylaldimines with 1-bromonitroalkanes

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