Pubblicazioni
Synthesis (1976), (2), 124-5.
The use of phase-transfer catalysis for the N-alkylation of indole
Barco, A.; Benetti, S.; Pollini, G. P.; Baraldi, P. G.
1-Alkylindoles were prepd. in 78-98% yields by alkylation of indole with alkyl sulfates, alkyl iodides, or alkyl bromides in a two-phase system of 50% aq. NaOH and C6H6 contg. Bu4N+HSO4-.
1-Alkylindoles were prepd. in 78-98% yields by alkylation of indole with alkyl sulfates, alkyl iodides, or alkyl bromides in a two-phase system of 50% aq. NaOH and C6H6 contg. Bu4N+HSO4-.
Pubblicazioni
Synthetic Communications (1977), 7(1), 13-17.
Synthesis of (±)15-hydroxy-prosta-2,4,8(12),13-tetraen-1-oic acid methyl estersfor the N-alkylation of indole
Barco, A.; Benetti, S.; Pollini, G. P.; Baraldi, P. G.; Guarneri, M.; Vicentini, C. B.araldi, P. G.
The synthesis of (±)-I and its 15-epimer from II (9 steps) was described.
The synthesis of (±)-I and its 15-epimer from II (9 steps) was described.
Pubblicazioni
Synthesis (1977), (12), 837.
Active γ-manganese dioxide promoted conversion of 4,5-dihydro-1,2-oxazoles to 1,2-oxazoles
Barco, A.; Benetti, S.; Pollini, G. P.; Baraldi, P. G.
Dehydrogenation of seven dihydrooxazoles I (R1 = Ph, octyl, Me, Ph, 2-naphthyl, CO2Me, hexyl; R2 = H, NO2; R3 = Me, Ph, (CH2)2CO2Me) with γ-MnO2 gave 97-100% oxazoles II.
Dehydrogenation of seven dihydrooxazoles I (R1 = Ph, octyl, Me, Ph, 2-naphthyl, CO2Me, hexyl; R2 = H, NO2; R3 = Me, Ph, (CH2)2CO2Me) with γ-MnO2 gave 97-100% oxazoles II.
Pubblicazioni
Synthetic Communications (1978), 8(4), 219-226.
Synthesis of 14-hydroxy-8-azaprostanoic acids methyl ester
Barco, A.; Benetti, S.; Pollini, G. P.; Veronesi, B.; Baraldi, P. G.; Guarneri, M.; Vicentini, C. B.
Several title compds., e.g., I, were prepd. via the key intermediate II [from O2N(CH2)3CO2Me, 1-octyne, and PhNCO], which via reductive cleavage, cyclization with ClCO2Et, and hydrogenation over Pd gave I.
Several title compds., e.g., I, were prepd. via the key intermediate II [from O2N(CH2)3CO2Me, 1-octyne, and PhNCO], which via reductive cleavage, cyclization with ClCO2Et, and hydrogenation over Pd gave I.
MOSTRA DI PIU'
Pubblicazioni
Journal of Medicinal Chemistry (1978), 21(9), 988-90.
Synthesis and prostaglandin-like activity of 2-(trans-3-hydroxy-1-octenyl)-3-indoleheptanoic acid
Barco, A.; Benetti, S.; Pollini, G. P.; Baraldi, P. G.; Guarneri, M.; Simoni, D.; Vicentini, C. B.; Borasio, P. G.; Capuzzo, A.
The title compd. (I) [67410-77-9] was prepd. from EtO2C(CH2)7CO2Et [624-17-9] in 12 steps via II . I contracted rat stomach fundus strips and guinea pig ileum prepns. at concns. 103 and 102 higher resp. than PGE1. I also stimulated rat liver aden...
The title compd. (I) [67410-77-9] was prepd. from EtO2C(CH2)7CO2Et [624-17-9] in 12 steps via II . I contracted rat stomach fundus strips and guinea pig ileum prepns. at concns. 103 and 102 higher resp. than PGE1. I also stimulated rat liver adenylate cyclase, but had a potency of 4-5 × 102 less than that of PGE1. I inhibited PGE1 activity in the latter system.
MOSTRA DI PIU'
Pubblicazioni
Journal of Organic Chemistry (1979), 44(10), 1734-6.
Synthesis of an 11-deoxy-8-azaprostaglandin E1 intermediate
Barco, Achille; Benetti, Simonetta; Pollini, Gian Piero; Baraldi, Pier Giovanni; Simoni, Daniele; Vicentini, Chiara Beatrice
Two different approaches to the synthesis of Me 7-(2-formyl-5-oxo-1-pyrrolidinyl)heptanoate (I), a synthon for the prepn. of 11-deoxy-8-azaprostaglandin E1, were described. The common feature was the generation of the crucial aldehydic group from th...
Two different approaches to the synthesis of Me 7-(2-formyl-5-oxo-1-pyrrolidinyl)heptanoate (I), a synthon for the prepn. of 11-deoxy-8-azaprostaglandin E1, were described. The common feature was the generation of the crucial aldehydic group from the styryl deriv. (II) by Lemieux-Johnson oxidn. The pyrrolidinone nucleus was secured in one case starting from the ω-carbinol lactam III contg. the N-linked α-C7 chain and in the other one employing the 3,5-disubstituted isoxazole intermediate IV.
MOSTRA DI PIU'
Pubblicazioni
Synthesis (1979), (1), 68-70.
Synthesis of 5-hydroxy-2-oxotetrahydropyrroles
Barco, A.; Benetti, S.; Pollini, G. P.; Baraldi, P. G.; Simoni, D.; Vicentini, C. B.
Treating cis- or trans-RNHCO(CH2)2CH:CH(CH2)2CONHR (I; R = H, Me2CHCH2CH2, PhCH2CH2, cyclohexyl, PhCHMe, Ph, p-MeOC6H4) in aq. dioxane with NaIO4 in the presence of OsO4 yielded 72-95% the hydroxypyrrolidinones II. I were prepd. by amidation of the ...
Treating cis- or trans-RNHCO(CH2)2CH:CH(CH2)2CONHR (I; R = H, Me2CHCH2CH2, PhCH2CH2, cyclohexyl, PhCHMe, Ph, p-MeOC6H4) in aq. dioxane with NaIO4 in the presence of OsO4 yielded 72-95% the hydroxypyrrolidinones II. I were prepd. by amidation of the corresponding acid chlorides.
MOSTRA DI PIU'
Pubblicazioni
Journal of Chemical Research, Synopses (1979), (5), 176-7.
A new, efficient synthesis of muscimol (5-ammoniomethylisoxazol-3-olate)
Barco, Achille; Benetti, Simonetta; Pollini, Gian Piero; Baraldi, Pier Giovanni; Guarneri, Mario
The title compd. (I) was prepd. in 84% overall yield from hydroxy ester II by sequential N-protection (dihydropyran, CH2Cl2-4-MeC6H4SO3H, 0°), redn. (NaBH4-MeOH, 0°), chlorination (CCl4-Ph3P reagent), deprotection (aq.-methanolic HCl) and ammonolys...
The title compd. (I) was prepd. in 84% overall yield from hydroxy ester II by sequential N-protection (dihydropyran, CH2Cl2-4-MeC6H4SO3H, 0°), redn. (NaBH4-MeOH, 0°), chlorination (CCl4-Ph3P reagent), deprotection (aq.-methanolic HCl) and ammonolysis (MeOH-NH3, 90°, 18 h).
MOSTRA DI PIU'
Pubblicazioni
Journal of Organic Chemistry (1979), 44(1), 105-6.
1,4-Diketones via isoxazole intermediates
Barco, A.; Benetti, S.; Pollini, G. P.; Baraldi, P. G.; Guarneri, M.; Vicentini, C. B.
Reductive ring cleavage of 3,5-disubstituted isoxazoles gave α,β-unsatd. 1,4-diketones. MeCOCH2CH2CO(CH2)5Me (I) was prepd. by 2 different routes: the masked isoxazoles II and III were converted to α,β-unsatd. ketones IV and MeCOCH2CH2COCH:CHBu,...
Reductive ring cleavage of 3,5-disubstituted isoxazoles gave α,β-unsatd. 1,4-diketones. MeCOCH2CH2CO(CH2)5Me (I) was prepd. by 2 different routes: the masked isoxazoles II and III were converted to α,β-unsatd. ketones IV and MeCOCH2CH2COCH:CHBu, which were selectively reduced with an Fe-based complex under mild conditions and then the protecting ketal group was removed to give I.
MOSTRA DI PIU'
Pubblicazioni
Journal of Organic Chemistry (1980), 45(15), 3141-2.
Use of [3 + 2] cycloaddition in elaboration of the ω chain of prostaglandins
Barco, Achille; Benetti, Simonetta; Pollini, Gian Piero; Baraldi, Pier Giovanni; Simoni, Daniele; Guarneri, Mario; Gandolfi, Carmelo
A new way of elaborating the target conjugated enone I, a key intermediate for the synthesis of 11-deoxy prostanoids, is described. A [3+2] cycloaddn. of the nitrile oxide generated from II and 1-heptyne provided the isoxazole scaffold destined to b...
A new way of elaborating the target conjugated enone I, a key intermediate for the synthesis of 11-deoxy prostanoids, is described. A [3+2] cycloaddn. of the nitrile oxide generated from II and 1-heptyne provided the isoxazole scaffold destined to become the ω-side chain of prostaglandins through reductive N-O bond cleavage.
MOSTRA DI PIU'
Pubblicazioni
Farmaco, Edizione Scientifica (1980), 35(8), 698-705.
Synthesis of compounds of antisecretory activity
Baraldi, P. G.; Dalla Vecchia, F.; Guarneri, M.; Vicentini, C. B.; Ceserani, R.
R-Ile-His-Pro-NH2 (I) and R-Lys(CO2CMe3)-Ile-His-Pro-NH2 (II) [R = 2-oxo-1-pyrrolidineheptanoyl, 1-(6-methoxycarbonylhexyl)-2-oxo-5-pyrrolidinecarbonyl, 3-indolylacyl] were prepd. by stepwise synthesis. I and II had antisecretory activity ≥15 time...
R-Ile-His-Pro-NH2 (I) and R-Lys(CO2CMe3)-Ile-His-Pro-NH2 (II) [R = 2-oxo-1-pyrrolidineheptanoyl, 1-(6-methoxycarbonylhexyl)-2-oxo-5-pyrrolidinecarbonyl, 3-indolylacyl] were prepd. by stepwise synthesis. I and II had antisecretory activity ≥15 times less than cimetidine.
MOSTRA DI PIU'
Pubblicazioni
International Journal of Peptide & Protein Research (1980), 16(1), 48-54.
Carboxyl activation in peptide synthesis using 4-oximino-pyrazol-5-ones
Vicentini, Chiara B.; Veronese, Augusto C.; Giori, Paolo; Baraldi, Pier Giovanni; Guarneri, Mario
The (E)- and (Z)-isomers of title pyrazolones I (R = Me Ph) were esterified with Z-Val-OH (Z = PhCH2O2C), Z-Gly-OH, and Ph3C-Gly-OH by dicyclohexylcarbodiimide (DCC) to give the appropriate active esters, which were used in peptide coupling reactions...
The (E)- and (Z)-isomers of title pyrazolones I (R = Me Ph) were esterified with Z-Val-OH (Z = PhCH2O2C), Z-Gly-OH, and Ph3C-Gly-OH by dicyclohexylcarbodiimide (DCC) to give the appropriate active esters, which were used in peptide coupling reactions. I were also used as additives in peptide coupling reactions by the DCC method. Several peptides were prepd. by the above methods in which racemization was not obsd. I were prepd. by treating pyrazolones II with amyl nitrite/HCl.
MOSTRA DI PIU'
Pubblicazioni
Journal of Organic Chemistry (1980), 45(23), 4776-8.
A new, elegant route to a key intermediate for the synthesis of 9(0)-methanoprostacyclin
Barco, Achille; Benetti, Simonetta; Pollini, Gian Piero; Baraldi, Pier Giovanni; Gandolfi, Carmelo
A new prepn. of the advanced intermediate I for the synthesis of 9(O)-methanoprostacyclin is described. The key step is an intramol. Michael addn. of a β-keto ester carbanion to an α,β-enone moiety II, which allows an easy construction of a suita...
A new prepn. of the advanced intermediate I for the synthesis of 9(O)-methanoprostacyclin is described. The key step is an intramol. Michael addn. of a β-keto ester carbanion to an α,β-enone moiety II, which allows an easy construction of a suitably functionalized bicyclo[3.3.0]octane system.
MOSTRA DI PIU'
Pubblicazioni
Synthesis (1981), (9), 727-9.
Synthesis of 6-substituted 3-methyl-1H-pyrazolo-[4,3-d]pyrimidine-7(6H)-ones
Baraldi, P. G.; Guarneri, M.; Moroder, F.; Simoni, D.; Benetti, S.
Aminopyrazoles I [R = NH2; R1 = C3-5 alkyl, (un)substituted phenylalkyl] underwent a cyclocondensation reaction with HCONH2 to yield title compds. II. Pyrazinodipyrazole deriv. III was treated with PrNH2 at room temp. to give I (R = NO2, R1 = Pr), w...
Aminopyrazoles I [R = NH2; R1 = C3-5 alkyl, (un)substituted phenylalkyl] underwent a cyclocondensation reaction with HCONH2 to yield title compds. II. Pyrazinodipyrazole deriv. III was treated with PrNH2 at room temp. to give I (R = NO2, R1 = Pr), which was reduced with NaBH4 and Pd/C to give I (R = NH2, R1 = Pr), which was heated with HCONH2 5 h at 180° to give II (R1 = Pr).
MOSTRA DI PIU'
Pubblicazioni
Synthesis (1981), (3), 199-200.
Prostanoid synthons: a new simple synthesis of butyl 5-oxocyclopentene-1-acetate and butyl 5-oxocyclopentene-1-heptanoate
Barco, A.; Benetti, S.; Baraldi, P. G.; Simoni, D.
1-Morpholinocyclopentene was refluxed with OHC(CH2)nCO2R (n = 0, R = Br; n = 5, R = Me) in cyclohexane 24 h with removal of H2O to give 79% and 66% resp., I, which were isomerized by heating with HCl-BuOH to give 95% and 93%, resp., II.
1-Morpholinocyclopentene was refluxed with OHC(CH2)nCO2R (n = 0, R = Br; n = 5, R = Me) in cyclohexane 24 h with removal of H2O to give 79% and 66% resp., I, which were isomerized by heating with HCl-BuOH to give 95% and 93%, resp., II.
MOSTRA DI PIU'
Pubblicazioni
Journal of Organic Chemistry (1981), 46(22), 4518-24.
Elaboration of the ω-chain of 11-deoxyprostanoid derivatives through isoxazole intermediates
Barco, Achille; Benetti, Simonetta; Pollini, Gian Piero; Baraldi, Pier Giovanni; Guarneri, Mario; Simoni, Daniele; Gandolfi, Carmelo
A new approach to the synthesis of 11-deoxyprostanoic acid derivs. entailed the use of 3,5-disubstituted isoxazoles as the source of the eight carbon atoms of the ω-chain. The key step involved formation of the C(13)-C(14) bond through a [3 + 2] cy...
A new approach to the synthesis of 11-deoxyprostanoic acid derivs. entailed the use of 3,5-disubstituted isoxazoles as the source of the eight carbon atoms of the ω-chain. The key step involved formation of the C(13)-C(14) bond through a [3 + 2] cycloaddn. of the nitrile oxides generated from 3β-(nitromethyl)-2α-substituted-cyclopentanone cycloethylene ketals to 1-heptyne to give the corresponding isoxazoles (e.g., I); the α-side chain was completed through Wittig condensation to give, e.g., II.
MOSTRA DI PIU'
Pubblicazioni
Journal of Medicinal Chemistry (1981), 24(5), 625-8.
Azaprostaglandin analogs. Synthesis and biological properties of 11-azaprostaglandin derivatives
Barco, Achille; Benetti, Simonetta; Pollini, Gian Piero; Baraldi, Pier Giovanni; Guarneri, Mario; Gandolfi, Carmelo; Ceserani, Roberto; Longiave, Daniela
Racemic I (R = H, Me) were prepd. by appropriate modifications of conventional methods. They did not possess improved prostaglandin activity (as compared with conventional prostaglandins) either in vitro or in vivo.
Racemic I (R = H, Me) were prepd. by appropriate modifications of conventional methods. They did not possess improved prostaglandin activity (as compared with conventional prostaglandins) either in vitro or in vivo.
MOSTRA DI PIU'
Pubblicazioni
Journal of the Chemical Society, Chemical Communications (1981), (12), 599-600.
3,5-Disubstituted isoxazoles as a latent aldol moiety: application to the synthesis of (±)-[6]-gingerol
Barco, Achille; Benetti, Simonetta; Baraldi, Pier Giovanni; Guarneri, Mario; Pollini, Gian Piero; Simoni, Daniele
The isoxazole I, prepd. (85%) by Wittig reaction of 3,4-MeO(PhCH2O)C6H3CHO and phosphonium salt II, was hydrogenated (prereduced PtO2, MeOH), amine protected (BzCl, pyridine, room temp., 12 h), then reduced (NaBH4, MeOH) to give the alc. III (R = PhC...
The isoxazole I, prepd. (85%) by Wittig reaction of 3,4-MeO(PhCH2O)C6H3CHO and phosphonium salt II, was hydrogenated (prereduced PtO2, MeOH), amine protected (BzCl, pyridine, room temp., 12 h), then reduced (NaBH4, MeOH) to give the alc. III (R = PhCH2O, R1 = NHBz, R2R3 = bond, R4 = H, R5 = OH)(IV). Treatment of IV with 90% aq. HOAc (0°, 2 h) followed by debenzoylation gave (±)-[6]-gingerol (III; R = R5 = OH, R1R2 = O, R3 = R4 = H).
MOSTRA DI PIU'
Pubblicazioni
Synthesis (1982), (1), 70-71.
Synthesis of 3-methyl-6-phenylamino-substituted-1H-pyrazolo[4,3-d]pyrimidine-7(6H)-ones
Baraldi, P. G.; Guarneri, M.; Moroder, F.; Simoni, D.; Vicentini, C. B.
Pyrazolopyrimidinones I (R = H, 4-Me, 3-Me, 2-MeO, 3-Cl, 2-Cl) were obtained by treating the diketopiperazine II with RC6H4NHNH2 to give III (R1 = NO2) which on hydrazinolysis gave III (R1 = NH2). The amines were cyclized to I with HCONH2.
Pyrazolopyrimidinones I (R = H, 4-Me, 3-Me, 2-MeO, 3-Cl, 2-Cl) were obtained by treating the diketopiperazine II with RC6H4NHNH2 to give III (R1 = NO2) which on hydrazinolysis gave III (R1 = NH2). The amines were cyclized to I with HCONH2.
MOSTRA DI PIU'
Pubblicazioni
Journal of Heterocyclic Chemistry (1982), 19(3), 557-60.
Synthesis of 2-(5-substituted isoxazol-3-yl)-4-oxo-3-thiazolidinyl alkanoic acids
Baraldi, P. G.; Simoni, D.; Moroder, F.; Manfredini, S.; Mucchi, L.; Dalla Vecchia, F.; Orsolini, P.
The isoxazolecarboxaldehydes I [R = Me, Me(CH2)4, Ph], prepd. in 3 steps from RCOCH2COCO2Et and NH2OH, were treated with H2N(CH2)nCO2Et (n = 1, 2, 5, 6) to give the Schiff bases II, which were treated with HSCH2CO2H followed by cyclization and hydrol...
The isoxazolecarboxaldehydes I [R = Me, Me(CH2)4, Ph], prepd. in 3 steps from RCOCH2COCO2Et and NH2OH, were treated with H2N(CH2)nCO2Et (n = 1, 2, 5, 6) to give the Schiff bases II, which were treated with HSCH2CO2H followed by cyclization and hydrolysis to give the title compds. III. None of the compds. showed bactericidal activity in vitro.
MOSTRA DI PIU'
