Histoire de Portugal : contenant les enterprises, navigations, & gestes memorables des Portugallois, tant en la cõqueste des Indes Orientales par eux descouvertes, qu'és guerres d'Afrique & autres exploits, depuis l'an mil quatre cens nonãte six, jusques à l'an mil cinq cens septante huit, sous Emmanuel premier, Jean troisieme, & Sebastian premier du nom / Pour Antoine Chuppin, ed. ; comprinse en vingt livres, dont les douze premiers sont traduits du latin de Ierosme Osorius, Euesque de Sylues en Algarve, les huit suivans prins de Lopez de Castagnede & d'autres historiensNouvellement mise en françois, par S.G.S. avec un discours du fruit qu'on peut recueillir de la lecture de cette histoire, & ample indice des matieres principales y contenues

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Synthesis of (±)-7,8-epoxy-4-basmen-6-one by a transannular cyclization strategy

The first synthesis of the cembranoid natural product (±)-7,8-epoxy-4-basmen-6- one (1) is described. Key steps of the synthetic route include the cationic cyclization of the acid chloride from 15 to provide the macrocycle 16, and the photochemical transannular radical cyclization of the ester 41 to form the tricyclic product 50. Product 50 was transformed into 1 in ten steps. Transition-state molecular modeling studies were found to provide accurate predictions of the structural and stereochemical outcomes of cyclization reactions explored experimentally in the development of the synthetic route to 1. These investigations should prove valuable in the development of transannular cyclization as a strategy for synthetic simplification.

Cyclization of citronellal to p-menthane-3,8-diols in water and carbon dioxide

A clean process has been developed for the synthesis of p-menthane-3,8-diols from cyclization of citronellal in CO2-H2O medium without any additives. With the addition of CO2, the reaction rate could be enhanced about 6 times for the cyclization of citronellal in H2O, because CO2 dissolved into water and formed carbonic acid inducing an increase of the acidity. Although, the reaction conversion in CO2-H2O is slightly lower compared to that obtained with sulfuric acid as catalyst, CO2-H2O could replace the sulfuric acid at a relative higher reaction temperature. The reaction kinetics studies showed that the hydration of isopulegols to p-menthane-3,8-diols is a reversible reaction. The equilibrium constant and the maximum equilibrium yield obtained in CO2-H2O at a range of CO2 pressures are similar to that with sulfuric acid catalyst.

PIFA-Mediated Oxidative Cyclization of 1-Carbamoyl-1-oximylcycloalkanes: Synthesis of Spiro-Fused Pyrazolin-5-one N-Oxides

convenient and efficient synthesis of spiro-fused pyrazolin-5-one N-oxides starting from readily available 1-carbamoyl-1-oximylcycloalkanes is developed. This general protocol features a novel and facile way for access to the five-membered azaheterocycles by formation of a new N-N single bond. The key cyclization step utilizes the formation of an N-oxonitrenium intermediate, mediated by the hypervalent iodine reagent PIFA, and its subsequent intramolecular trapping by the amide moiety under rather mild experimental conditions.

Efficient synthesis of highly substituted pyrrolin-4-ones via PIFA-mediated cyclization reactions of enaminones

A convenient and efficient synthesis of highly substituted pyrrolin-4-ones is developed via the PIFA-mediated cyclization reactions of readily available enaminones, and a mechanism involving sequential cleavage of N-C bond, formation of new N-C bond, intramolecular addition reaction, and benzilic acid type rearrangement is proposed.

Cationic cyclization of neoprene with a diethylaluminum chloride and organic chloride catalyst system

The cyclization of neoprene was achieved with the aid of a cationic catalyst system based on diethylaluminum chloride (Et2AlCl) and an organic chloride, allyl chloride (CH2=CHCH2Cl) or benzyl chloride (C6H5CH2Cl). The main parameters of the cyclization process were investigated. Elastomers with low intrinsic viscosity, ready solubility and some gelling were obtained. Xylene was a good solvent for the cyclization process, which took place in a very short time (less than or equal to5 min). The products were characterized with IR, H-1-NMR, differential scanning calorimetry, and gel permeation chromatography. The polycyclic structure was determined. The degree of cyctization and the incorporated solvent content were estimated with a H-1-NMR method.

Study on the cyclization of cis-1,4 polybutadiene in various solvents and its mechanism

The cyclization of cis-1,4 polybutadiene in various solvents (mesitylene,xylene, toluene,benzene and cyclohexane) with the catalyst composed of CH2=CHCH2Cl-AlEt2Cl was studied. The infrared spectra of the cyclized products were investigated. It was shown that the products produced in cyclohexane and mesitylene have infrared spectra identical with those of the original cis-1,4-polybutadiene and the products obtained in other aromatics have infrared spectra different from each other and distinguishing with those of the parent cis-1,4 polybutadiene. The analyses of infrared spectra came to the conclusion that the molecules of aromatic solvent participate in cyclization of cis-1,4 polybutadiene at the given condition. A possible reaction scheme involving an electrophilic substitution of carbonium ions for Ar-H of aromatic solvents was proposed. Some experimental facts were explained with great satisfaction on the basis of the above mechanism.

Cyclization in situ of isoprene polymerization catalyzed by Nd-Al bimetallic complex

Function of chloride and effect of various alkylaluminiums, C1/A1 molar ratio, solvents on cyclization in situ of isoprene polymerization catalyzed by Nd-Al bimetallic complex were studied. The structure of cyclized products was characterized by means of IR and H-1 NMR, The results indicated that in the course of isoprene polymerization with rare earth catalytic system, the function of alkylchloride introduced is terminating cis-polymerization and generating cationic species with alkyl-aluminums to initiate cyclization in situ. Soluble cyclized polyisoprene was obtained with fragments of cyclopolyisoprene.

Cationic cyclization of styrene-butadiene rubber

Controlled cyclization of styrene-butadiene rubber (SBR) was achieved with the aid of cationic catalyst system based on diethylaluminium chloride (AIEt(2)Cl) and benzyl chloride (C6H5CH2Cl) and by working in xylene solution at high temperature (T > 100 degreesC). The main parameters of the cyclization process were investigated. Elastomers with low intrinsic viscosity, ready solubility, free gel were obtained. The products were characterized with IR H-1-NMR, DSC, GPC. The polycyclic structure was determined. (C) 2001 Published by Elsevier Science Ltd.

THEORETICAL-STUDIES ON THE CYCLIZATION PROCESS OF A NEW ORGANOSULFUR REACTION

The cyclization process of a new organosulfur reaction was studied by the MNDO (UHF) method. The first reaction path was assumed to be via the organosulfur radical intermediate, the second via the ionic (cationic and anionic) intermediates. The dehydroxylation process was assumed to occur with the synergistic cyclization. The results obtained indicate that the potential energy barrier of the first reaction path was about 102 kcal mol(-1), and although the formation of the ionic intermediate is comparatively difficult, the potential energy barrier of the second path is comparable to the first. The sequential reaction path via the radical intermediate, i.e. first cyclization, then dehydroxylation, was investigated for comparison. The cyclization reaction was found to be the thermodynamically favored process, while the ensuing dehydroxylation process was found to have a potential energy barrier of about 62 kcal mol(-1).

Synthesis of highly substituted pyrrolidines via palladium-catalyzed cyclization of 5-vinyloxazolidinones and activated alkenes

N-Tosyl-5,5-divinyloxazolidin-2-one undergoes a palladium-catalyzed decarboxylative cyclization across a range of electrophilic alkenes to give the corresponding pyrrolidine derivatives bearing two contiguous quaternary centres. Alkenes bearing two electron-withdrawing groups are required; pyrrolidines were not formed from mono-activated alkenes. Bulky, electron-rich phosphines promote pyrrolidine formation with less highly electrophilic, doubly activated alkenes, and a dramatic improvement is observed in the presence of iodide.

A study of Heck cyclization reactions to form phenanthridine ring systems

A survey of conditions for the palladium catalyzed intramol. Heck cyclization of protected amines has shown that the Herrmann-Beller palladacycle can be exploited under 'cationic' conditions to provide a robust and rapid route (

PALLADIUM CATALYZED TANDEM CYCLIZATION-ANION CAPTURE PROCESSES .1. BACKGROUND AND HYDRIDE ION CAPTURE BY ALKYL-PALLADIUM AND PI-ALLYL-PALLADIUM SPECIES

A new, wide ranging, synthetically powerful, catalytic tandem cyclisation-anion capture process is proposed which depends on the rate of cyclisation of an organopalladium specifies (RPdX) onto a proximate alkene or diene being significantly faster than anion exchange and reductive elimination in the sequence RPdX --> RPdY --> RY + Pd(0). The catalytic cyclisation - anion capture sequence is illustrated for hydride capture by a wide variety of substrates giving rise to fused- and spiro-, carbo- and hetero-cyclic systems, regio- and stereo-specifically.