Nevertheless, the one-pot synthesis of 4-aryl and 4-vinylquinolines 4 starting from 1 represents ... more Nevertheless, the one-pot synthesis of 4-aryl and 4-vinylquinolines 4 starting from 1 represents a more interesting challenge. [17] In order to achieve this goal , we investigated the development of a one-pot/two-step synthetic protocol. NaI (2 equiv) was added to 1a in ethanol at 80 °C ...
ABSTRACT Vinyl and aryl triflates react with methyl α-acetamidoacrylate in the presence of cataly... more ABSTRACT Vinyl and aryl triflates react with methyl α-acetamidoacrylate in the presence of catalytic amounts of palladium to give ß-vinyl and ß-aryl-αß-didehydro-α-aminoacid derivatives in good to high yields. A variety of reaction conditions were examined. Vinyl triflates give good results in the presence of both Pd(OAc)2(PPh3)2/n-Bu3N and Pd(OAc)2/NaHCO3/n-BU4NCl. In most cases however because of simplicity high yields and reaction rate the Pd(OAc)2/AcOK combination appears to be the system of choice. The behaviour of aryl triflates is less homogeneous. Best results were obtained in the presence of the Pd(OAc)2/n-Bu3N/DPPF/LiCl and Pdt(OAc)2/NaHCO3/n-Bu4NCl systems.
ABSTRACT ChemInform is a weekly Abstracting Service, delivering concise information at a glance t... more ABSTRACT ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
The palladium(O)-catalysed coupling of aryl and vinyl triflates or halides with the easily availa... more The palladium(O)-catalysed coupling of aryl and vinyl triflates or halides with the easily available 2-ethynylaniline, followed by a palladium(IIl-catalysed cyclization step, provides an efficient and very versatile procedure for the synthesis of functionalyzed E-substituted indoles.
... 9) m (B) -(CHg) 4~ HC ^d 54 ( -, 6) n (A) Et Me H 24 56 ( -, 9) 0 (A) Me Me H 24 55 ( -, 6) P... more ... 9) m (B) -(CHg) 4~ HC ^d 54 ( -, 6) n (A) Et Me H 24 56 ( -, 9) 0 (A) Me Me H 24 55 ( -, 6) P (B)MeO' 4-MeO0 12 ... In some cases it is possible and convenient to carry out the reductive arylation of the carbon-carbon triple bond by simply adding the palladium catalyst, the base, the ...
Fused pyridine derivatives Fused pyridine derivatives R 0450 An Efficient Synthesis of 2,4-Substi... more Fused pyridine derivatives Fused pyridine derivatives R 0450 An Efficient Synthesis of 2,4-Substituted [1,8]Naphthyridines from 3-(2-Amino-5-methylpyridin-3-yl)-1-arylprop-2-yn-1-ones.-2,4-Disubstituted [1,8]naphthyridines (VI), (VIII), (X) and (XII) are obtained in good yields from the propynones (IV) and nucleophiles (V), (VII), (IX) and (XI) via a domino conjugate addition-annulation reaction. The starting propynones (IV) are prepared by a Pd-catalyzed carbonylative coupling of the silylacetylenes (I) with aryl iodides (II).
A variety of 5-vinyl-4-pentynoic acids (12 examples) have been prepared in good to high yield by ... more A variety of 5-vinyl-4-pentynoic acids (12 examples) have been prepared in good to high yield by reacting vinyl triflates (1-cycloalkenyl trifluoromethanesulfonates) and 4-pentynoic acid at room temperature in dimethyl sulfoxide in the presence of diethylamine or ...
Disubstituted-2(1H)-quinolones have been prepared through a procedure based on the palladium-cata... more Disubstituted-2(1H)-quinolones have been prepared through a procedure based on the palladium-catalysed reaction of the readily available ethyl N-(o-ethynyl))malonanilide with aryl, heteroaryl and vinyl halides or vinyl triflates followed by the cyclization of the resulting coupling derivatives under basic conditions. It is shown that 3,4-disubstituted-2(1H)-quinolones are useful synthetic intermediates for the preparation of 3,4-disubstituted-and 2,3,4-trisubstituted quinolines. The construction of heterocyclic derivatives based upon the concept of palladium-catalysed coupling/cyclization of alkyne bearing a proximate (pro)nucleophile has proved to be a versatile and efficient synthetic methodology.l'2 Our continuing interest in this area, and our involvement in a program designed to identify novel non-nucleoside 2(1H)-quinolone-based anti-AIDS agents, led us to investigate the utilization of this methodology for the preparation of substituted 2(lH)quinolones.3 In particular, we decided to evaluate the employment of ethyl N-(o-ethynyl)malonanilide 1 as the starting building block. This compound can be readily prepared in 80Vo overall yield from oiodoaniline through a one-pot three-step procedure.4 Now we report that compound I reacts with aryl, heteroaryl and vinyl halides or triflates 2 to afford the coupling derivatives 35 and that subsequent treatment of 3 with NaH or KOr-Bu in DMSO leads to the formation of the 3,4-disubstituted-2(lH)-quinolones 4 through an intramolecular carbocyclization6 lScheme 1).
Cholesta-3,5dien-3-yl triflate and androsta-16en-17-yl iodide were vinylated with palladium and t... more Cholesta-3,5dien-3-yl triflate and androsta-16en-17-yl iodide were vinylated with palladium and the olefins hydrofotmylated in the presence of rhodium and platinum catalysts. Till now there are very few examples for the functionalization of steroids via homogeneous carbonylationt and coupling reactions. Lately en01 triflates derived from keto-steroids have been used for the j3-vinylation of vinyl acetate in the presence of palladium catalysts 2. An additional possibility for the vinylation is the cross-coupling reactionof enol-triflates and vinyl-stannanes3. Indeed, to our knowledge, no example for the Stille-coupling using steroids has been reported so far. p.759; B.Fell in Houben-Weyl Methoden der Organischen Chemie, E 18/2. Georg ThiemeVerlag. Stuttgart, 1986, p.779 7. The mixture of the formyl-products were analyzed by GC-MS and 'H NMR.
PergamonTetrahedron 55 (1999)1323313250 Synthesis of Functionalised Quinolines through Tandem Add... more PergamonTetrahedron 55 (1999)1323313250 Synthesis of Functionalised Quinolines through Tandem Addition Annulation Reactions of (2Aminophenyl)a,Ynones Antonio Arcadia, Fabio Marinellia, Elisabetta Rossib TETRAHEDRON ' Dipartimento di Cbimica Ingegneria ...
Nevertheless, the one-pot synthesis of 4-aryl and 4-vinylquinolines 4 starting from 1 represents ... more Nevertheless, the one-pot synthesis of 4-aryl and 4-vinylquinolines 4 starting from 1 represents a more interesting challenge. [17] In order to achieve this goal , we investigated the development of a one-pot/two-step synthetic protocol. NaI (2 equiv) was added to 1a in ethanol at 80 °C ...
ABSTRACT Vinyl and aryl triflates react with methyl α-acetamidoacrylate in the presence of cataly... more ABSTRACT Vinyl and aryl triflates react with methyl α-acetamidoacrylate in the presence of catalytic amounts of palladium to give ß-vinyl and ß-aryl-αß-didehydro-α-aminoacid derivatives in good to high yields. A variety of reaction conditions were examined. Vinyl triflates give good results in the presence of both Pd(OAc)2(PPh3)2/n-Bu3N and Pd(OAc)2/NaHCO3/n-BU4NCl. In most cases however because of simplicity high yields and reaction rate the Pd(OAc)2/AcOK combination appears to be the system of choice. The behaviour of aryl triflates is less homogeneous. Best results were obtained in the presence of the Pd(OAc)2/n-Bu3N/DPPF/LiCl and Pdt(OAc)2/NaHCO3/n-Bu4NCl systems.
ABSTRACT ChemInform is a weekly Abstracting Service, delivering concise information at a glance t... more ABSTRACT ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
The palladium(O)-catalysed coupling of aryl and vinyl triflates or halides with the easily availa... more The palladium(O)-catalysed coupling of aryl and vinyl triflates or halides with the easily available 2-ethynylaniline, followed by a palladium(IIl-catalysed cyclization step, provides an efficient and very versatile procedure for the synthesis of functionalyzed E-substituted indoles.
... 9) m (B) -(CHg) 4~ HC ^d 54 ( -, 6) n (A) Et Me H 24 56 ( -, 9) 0 (A) Me Me H 24 55 ( -, 6) P... more ... 9) m (B) -(CHg) 4~ HC ^d 54 ( -, 6) n (A) Et Me H 24 56 ( -, 9) 0 (A) Me Me H 24 55 ( -, 6) P (B)MeO' 4-MeO0 12 ... In some cases it is possible and convenient to carry out the reductive arylation of the carbon-carbon triple bond by simply adding the palladium catalyst, the base, the ...
Fused pyridine derivatives Fused pyridine derivatives R 0450 An Efficient Synthesis of 2,4-Substi... more Fused pyridine derivatives Fused pyridine derivatives R 0450 An Efficient Synthesis of 2,4-Substituted [1,8]Naphthyridines from 3-(2-Amino-5-methylpyridin-3-yl)-1-arylprop-2-yn-1-ones.-2,4-Disubstituted [1,8]naphthyridines (VI), (VIII), (X) and (XII) are obtained in good yields from the propynones (IV) and nucleophiles (V), (VII), (IX) and (XI) via a domino conjugate addition-annulation reaction. The starting propynones (IV) are prepared by a Pd-catalyzed carbonylative coupling of the silylacetylenes (I) with aryl iodides (II).
A variety of 5-vinyl-4-pentynoic acids (12 examples) have been prepared in good to high yield by ... more A variety of 5-vinyl-4-pentynoic acids (12 examples) have been prepared in good to high yield by reacting vinyl triflates (1-cycloalkenyl trifluoromethanesulfonates) and 4-pentynoic acid at room temperature in dimethyl sulfoxide in the presence of diethylamine or ...
Disubstituted-2(1H)-quinolones have been prepared through a procedure based on the palladium-cata... more Disubstituted-2(1H)-quinolones have been prepared through a procedure based on the palladium-catalysed reaction of the readily available ethyl N-(o-ethynyl))malonanilide with aryl, heteroaryl and vinyl halides or vinyl triflates followed by the cyclization of the resulting coupling derivatives under basic conditions. It is shown that 3,4-disubstituted-2(1H)-quinolones are useful synthetic intermediates for the preparation of 3,4-disubstituted-and 2,3,4-trisubstituted quinolines. The construction of heterocyclic derivatives based upon the concept of palladium-catalysed coupling/cyclization of alkyne bearing a proximate (pro)nucleophile has proved to be a versatile and efficient synthetic methodology.l'2 Our continuing interest in this area, and our involvement in a program designed to identify novel non-nucleoside 2(1H)-quinolone-based anti-AIDS agents, led us to investigate the utilization of this methodology for the preparation of substituted 2(lH)quinolones.3 In particular, we decided to evaluate the employment of ethyl N-(o-ethynyl)malonanilide 1 as the starting building block. This compound can be readily prepared in 80Vo overall yield from oiodoaniline through a one-pot three-step procedure.4 Now we report that compound I reacts with aryl, heteroaryl and vinyl halides or triflates 2 to afford the coupling derivatives 35 and that subsequent treatment of 3 with NaH or KOr-Bu in DMSO leads to the formation of the 3,4-disubstituted-2(lH)-quinolones 4 through an intramolecular carbocyclization6 lScheme 1).
Cholesta-3,5dien-3-yl triflate and androsta-16en-17-yl iodide were vinylated with palladium and t... more Cholesta-3,5dien-3-yl triflate and androsta-16en-17-yl iodide were vinylated with palladium and the olefins hydrofotmylated in the presence of rhodium and platinum catalysts. Till now there are very few examples for the functionalization of steroids via homogeneous carbonylationt and coupling reactions. Lately en01 triflates derived from keto-steroids have been used for the j3-vinylation of vinyl acetate in the presence of palladium catalysts 2. An additional possibility for the vinylation is the cross-coupling reactionof enol-triflates and vinyl-stannanes3. Indeed, to our knowledge, no example for the Stille-coupling using steroids has been reported so far. p.759; B.Fell in Houben-Weyl Methoden der Organischen Chemie, E 18/2. Georg ThiemeVerlag. Stuttgart, 1986, p.779 7. The mixture of the formyl-products were analyzed by GC-MS and 'H NMR.
PergamonTetrahedron 55 (1999)1323313250 Synthesis of Functionalised Quinolines through Tandem Add... more PergamonTetrahedron 55 (1999)1323313250 Synthesis of Functionalised Quinolines through Tandem Addition Annulation Reactions of (2Aminophenyl)a,Ynones Antonio Arcadia, Fabio Marinellia, Elisabetta Rossib TETRAHEDRON ' Dipartimento di Cbimica Ingegneria ...
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