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Michael M Silaev - One of the best experts on this subject based on the ideXlab platform.
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the radical chain addition to double molecular bonds by the nonbranched chain mechanism low reactive free radicals shortening kinetic chains
Journal of Applied Solution Chemistry and Modeling, 2014Co-Authors: Michael M SilaevAbstract:Five reaction schemes are suggested for the initiated nonbranched-chain addition of free radicals to the multiple bonds of the Unsaturated Compounds. The proposed schemes include the reaction competing with chain propagation reactions through a reactive free radical. The chain evolution stage in these schemes involves three or four types of free radicals. One of them is relatively low-reactive and inhibits the chain process by shortening of the kinetic chain length. Based on the suggested schemes, nine rate equations (containing one to three parameters to be determined directly) are deduced using quasi-steady-state treatment. These equations provide good fits for the nonmonotonic (peaking) dependences of the formation rates of the molecular products (1:1 adducts) on the concentration of the Unsaturated component in binary systems consisting of a saturated component (hydrocarbon, alcohol, etc.) and an Unsaturated component (olefin, allyl alcohol, formaldehyde, or dioxygen). The Unsaturated Compound in these systems is both a reactant and an autoinhibitor generating low-reactive free radicals. A similar kinetic description is applicable to the nonbranched-chain process of the free-radical hydrogen oxidation, in which the oxygen with the increase of its concentration begins to act as an oxidation autoingibitor (or an antioxidant). The energetics of the key radical-molecule reactions is considered.
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kinetics of nonbranched chain processes of the free radical addition with reactions in which the 1 1 adduct radicals compete for interaction with saturated and Unsaturated components of the binary reaction system
Global Journal of Science Frontier Research, 2013Co-Authors: Michael M SilaevAbstract:Five reaction schemes are suggested for the initiated nonbranched-chain addition of free radicals to the multiple bonds of the Unsaturated Compounds. The proposed schemes include the reaction competing with chain propagation reactions through a reactive free radical. The chain evolution stage in these schemes involves three or four types of free radicals. One of them is relatively low-reactive and inhibits the chain process by shortening of the kinetic chain length. Based on the suggested schemes, nine rate equations (containing one to three parameters to be determined directly) are deduced using quasi-steady-state treatment. These equations provide good fits for the nonmonotonic (peaking) dependences of the formation rates of the molecular products (1:1 adducts) on the concentration of the Unsaturated component in binary systems consisting of a saturated component (hydrocarbon, alcohol, etc.) and an Unsaturated component (olefin, allyl alcohol, formaldehyde, or dioxygen). The Unsaturated Compound in these systems is both a reactant and an autoinhibitor generating low-reactive free radicals. A similar kinetic description is applicable to the nonbranched-chain process of the free-radical hydrogen oxidation, in which the oxygen with the increase of its concentration begins to act as an oxidation autoingibitor (or an antioxidant). The energetics of the key radical-molecule reactions is considered.
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kinetics of nonbranched chain processes of the free radical addition in the binary reaction systems with saturated and Unsaturated components that compete for interaction with the resulting 1 1 adduct radicals
Universal Journal of Chemistry, 2013Co-Authors: Michael M SilaevAbstract:Five reaction schemes are suggested for the initiated nonbranched-chain addition of free radicals to the multiple bonds of the Unsaturated Compounds. The proposed schemes include the reaction competing with chain propagation reactions through a reactive free radical. The chain evolution stage in these schemes involves three or four types of free radicals. One of them is relatively low-reactive and inhibits the chain process by shortening of the kinetic chain length. Based on the suggested schemes, nine rate equations (containing one to three parameters to be determined directly) are deduced using quasi-steady-state treatment. These equations provide good fits for the nonmonotonic (peaking) dependences of the formation rates of the molecular products (1:1 adducts) on the concentration of the Unsaturated component in binary systems consisting of a saturated component (hydrocarbon, alcohol, etc.) and an Unsaturated component (olefin, allyl alcohol, formaldehyde, or dioxygen). The Unsaturated Compound in these systems is both a reactant and an autoinhibitor generating low-reactive free radicals. A similar kinetic description is applicable to the nonbranched-chain process of the free-radical hydrogen oxidation, in which the oxygen with the increase of its concentration begins to act as an oxidation autoingibitor (or an antioxidant). The energetics of the key radical-molecule reactions is considered.
Ghirardi Elena - One of the best experts on this subject based on the ideXlab platform.
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Enantio- and Diastereoselective Cyclocondensation Reactions. Stereocontrolled Access to Azabicycles and Application to Natural Product Synthesis
'Edicions de la Universitat de Barcelona', 2016Co-Authors: Ghirardi ElenaAbstract:The first objective of this Thesis was the study of the preparation of octhydro-1H-cyclopenta[b]pyridines and octahydro-1H-indoles, through the synthesis of (R)-phenylglycinol derived tricyclic lactams. Following the previous reported methodology a carbon substituent would be present at the carbocyclic ring and we planned to find the conditions for controlling its absolute configuration. Unfortunately, the reaction of ketoester 4 and ketoacid 7, provided undesired enamines 8 and 9. On the other hand, the reaction of ketoacid derivatives 16 and 17 with (R)-phenylglycinol led to a mixture of epimeric amides 18. With the aim to extend the methodology, we planned to study the cyclocondensation reaction of (R)-phenylglycinol and (1S, 2R)-aminoindanol with C-3 and C-5 substituted cyclohexanepropionate derivatives. These reactions provided enantiopure tricyclic or pentacyclic lactams: in every run, a major lactam was isolated or identified, and a minor one was detected. The use of (1S, 2R)-aminoindanol resulted in better results. These tricyclic and pentacyclic lactams are precursors of C-8 (and C-6,8) substituted cis-decahydroquinolines. The conversion required the stereoselective reductive cleavage of C-O oxazolidine bond with simultaneous reduction of lactam carbonyl group, and debenzylation. A library of enantiopure cis-decahydroquinolines was obtained. To illustrate the usefulness of our method, we decided to undertake the synthesis of some alkaloids of Myrioneuron nutans family, which contain an 8-substituted cis-decahydroquinoline core. In particular, we prepared the enantiopure alcohol 82, which was described to be a common intermediate in the synthesis of various Mirioneuron nutans alkaloids. Our synthetic procedure greatly improved the previous results reported for the synthesis of this alcohol. The cyclocondensation reaction of (R)-phenylglycinol and (1S,2R)-aminoindanol with 3-alkyl-2-oxo-cyclohexane-1-acetate derivatives was finally considered. Reaction of (R)-phenylglycinol and 3-alkyl-2-oxocyclohexaneacetate derivatives 97-100 and 107 provided with high yield and stereoselectivity tricyclic lactams 110, 112a, 114, 116 and 118, which incorporate an alkyl or aryl substituent at C-10, while (1S,2R)-aminoindanol did not furnish so good outcomes. These reactions stereoselectively provided an additional minor hexahydroindole by-product. The absolute configuration of these Compounds 111a, 113a, 115a and 117a was confirmed by X-ray crystallography. In the case of any or aryl substituent at C-10 of the tricyclic lactam, no by products were detected. We demonstrated that these Unsaturated products derived from the opening of the oxazolidine ring of the minor lactams, which are epimers at C-10 of the major lactams, in the presence of acids. The stereoselective opening of the oxazolidine ring of the major lactams, in the presence of strong acids provided Unsaturated Compounds 111b, 113b, 115b and 117b, in which H-7 and H-7a resulted in cis relative disposition. In the case of lactam 118, with an aryl substituent at C-10, provided the Unsaturated Compound 125, in which H-7 and H-7a are in relative trans disposition. This different relative configuration can be accounted for by considering the structure rigidity of this system. Major tricyclic lactams were converted into C-7 exo substituted cis-octahydroindoles and cis-octahydroindolones, by selection of the appropriate reductive conditions. Hexahydroindolones 111b, 113b, 115b and 117b were converted stereoselectively into the corresponding enantiopure C-7 endo substituted cis-octahydroindolones, by catalytic hydrogenation of the carbon-carbon double bond, followed by elimination of the chiral inductor through reaction with sodium radical. Moreover, these hexahydroindolones and 125 were transformed into the corresponding trans-octahydroindolones 146c-149c and 126b by simultaneous reduction and debenzylation in sodium ammonia. The presence of the amide function allowed the stereoselective insertion of a new substituent by a-alkylation and a-amidoalkylation. Finally, in order to demonstrate the utility of this methodology, (+)-a-Lycorane was synthesized in only four steps, starting from easily available ketone 171, in 35% of overall yield, which resulted an improvement with respect to previously reported synthesis.El primer objetivo de esta Tesis Doctoral ha sido el estudio de la preparación de octahidro-1H-ciclopentapiridinas y octahidro-1H-indoles, a través de la síntesis de lactamas tricíclicas derivadas del (R)-fenilglicinol. Desafortunadamente, la reacción del ceto-éster 4 y del ceto-ácido 7, proporcionó solamente las eniminas 8 y 9. Por otro lado, la reacción de los derivados de ceto-ácidos 16 y 17 con (R)-fenilglicinol rindió únicamente una mezcla de productos 18, amidas conjugadas epímeras en la posición C-7a. Se ha sido estudiado la reacción de ciclocondensación de derivados de 2-oxociclohexano propionato convenientemente sustituidos en C-3 o en C-3 y C-5 con (R)-fenilglicinol y (1S,2R)-aminoindanol. Esta reacción conduce estereoselectivamente a lactamas tricíclicas o pentacíclicas quirales: se aisló mayoritariamente una lactama y se detectó la presencia de otra minoritaria. Al utilizar (1S,2R)-aminoindanol se obtuvieron mejores resultados. Estas lactamas son precursoras de cis-decahidroquinolinas, con sustituyentes en la posición 8 o en la posición 6 y 8. Las etapas clave de esta transformación son la reducción con alano y la eliminación del inductor quiral. Con esta metodología se ha preparado la decahidroquinolina 82, precursor de numerosos alcaloides de la familia Mirioneuron nutans. Además, presentamos el estudio de las reacciones de ciclocondensación con (R)-fenilglicinol a partir de ciclohexanonas que poseen una cadena de acetato en la posición C-1 y diversos sustituyentes alquilo o arilo en la posición C-3. Esta reacción conduce estereoselectivamente a una sola lactama tricíclica de las ocho posibles. A partir de las cetonas con un sustituyente alquilo en la posición C-3 aislamos una cantidad variable de enamida. Las lactamas mayoritarias, fueron convertidas en cis-octahidroindoles y cis-octahidroindolonas, que presentan un sustituyente en la posición 7 o en las posiciones 7 y 7a del anillo carbocíclico. Además, estudiamos la reactividad de las lactamas tricíclicas en medio ácido: la reacción con TiCl4 en THF, proporciona lactamas insaturadas con elevada estereoselectividad y buen rendimiento. La presencia de la función enamida, nos permitió preparar selectivamente nuevas cis y trans octahidroindolonas. Esta metodología nos permitió sintetizar el (a)-Licorano, un metabolito de la familia de las Amaryllidaceae
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Enantio- and Diastereoselective Cyclocondensation Reactions. Stereocontrolled Access to Azabicycles and Application to Natural Product Synthesis
'Edicions de la Universitat de Barcelona', 2016Co-Authors: Ghirardi ElenaAbstract:[eng] The first objective of this Thesis was the study of the preparation of octhydro-1H-cyclopenta[b]pyridines and octahydro-1H-indoles, through the synthesis of (R)-phenylglycinol derived tricyclic lactams. Following the previous reported methodology a carbon substituent would be present at the carbocyclic ring and we planned to find the conditions for controlling its absolute configuration. Unfortunately, the reaction of ketoester 4 and ketoacid 7, provided undesired enamines 8 and 9. On the other hand, the reaction of ketoacid derivatives 16 and 17 with (R)-phenylglycinol led to a mixture of epimeric amides 18. With the aim to extend the methodology, we planned to study the cyclocondensation reaction of (R)-phenylglycinol and (1S, 2R)-aminoindanol with C-3 and C-5 substituted cyclohexanepropionate derivatives. These reactions provided enantiopure tricyclic or pentacyclic lactams: in every run, a major lactam was isolated or identified, and a minor one was detected. The use of (1S, 2R)-aminoindanol resulted in better results. These tricyclic and pentacyclic lactams are precursors of C-8 (and C-6,8) substituted cis-decahydroquinolines. The conversion required the stereoselective reductive cleavage of C-O oxazolidine bond with simultaneous reduction of lactam carbonyl group, and debenzylation. A library of enantiopure cis-decahydroquinolines was obtained. To illustrate the usefulness of our method, we decided to undertake the synthesis of some alkaloids of Myrioneuron nutans family, which contain an 8-substituted cis-decahydroquinoline core. In particular, we prepared the enantiopure alcohol 82, which was described to be a common intermediate in the synthesis of various Mirioneuron nutans alkaloids. Our synthetic procedure greatly improved the previous results reported for the synthesis of this alcohol. The cyclocondensation reaction of (R)-phenylglycinol and (1S,2R)-aminoindanol with 3-alkyl-2-oxo-cyclohexane-1-acetate derivatives was finally considered. Reaction of (R)-phenylglycinol and 3-alkyl-2-oxocyclohexaneacetate derivatives 97-100 and 107 provided with high yield and stereoselectivity tricyclic lactams 110, 112a, 114, 116 and 118, which incorporate an alkyl or aryl substituent at C-10, while (1S,2R)-aminoindanol did not furnish so good outcomes. These reactions stereoselectively provided an additional minor hexahydroindole by-product. The absolute configuration of these Compounds 111a, 113a, 115a and 117a was confirmed by X-ray crystallography. In the case of any or aryl substituent at C-10 of the tricyclic lactam, no by products were detected. We demonstrated that these Unsaturated products derived from the opening of the oxazolidine ring of the minor lactams, which are epimers at C-10 of the major lactams, in the presence of acids. The stereoselective opening of the oxazolidine ring of the major lactams, in the presence of strong acids provided Unsaturated Compounds 111b, 113b, 115b and 117b, in which H-7 and H-7a resulted in cis relative disposition. In the case of lactam 118, with an aryl substituent at C-10, provided the Unsaturated Compound 125, in which H-7 and H-7a are in relative trans disposition. This different relative configuration can be accounted for by considering the structure rigidity of this system. Major tricyclic lactams were converted into C-7 exo substituted cis-octahydroindoles and cis-octahydroindolones, by selection of the appropriate reductive conditions. Hexahydroindolones 111b, 113b, 115b and 117b were converted stereoselectively into the corresponding enantiopure C-7 endo substituted cis-octahydroindolones, by catalytic hydrogenation of the carbon-carbon double bond, followed by elimination of the chiral inductor through reaction with sodium radical. Moreover, these hexahydroindolones and 125 were transformed into the corresponding trans-octahydroindolones 146c-149c and 126b by simultaneous reduction and debenzylation in sodium ammonia. The presence of the amide function allowed the stereoselective insertion of a new substituent by a-alkylation and a-amidoalkylation. Finally, in order to demonstrate the utility of this methodology, (+)-a-Lycorane was synthesized in only four steps, starting from easily available ketone 171, in 35% of overall yield, which resulted an improvement with respect to previously reported synthesis.[spa] El primer objetivo de esta Tesis Doctoral ha sido el estudio de la preparación de octahidro-1H-ciclopentapiridinas y octahidro-1H-indoles, a través de la síntesis de lactamas tricíclicas derivadas del (R)-fenilglicinol. Desafortunadamente, la reacción del ceto-éster 4 y del ceto-ácido 7, proporcionó solamente las eniminas 8 y 9. Por otro lado, la reacción de los derivados de ceto-ácidos 16 y 17 con (R)-fenilglicinol rindió únicamente una mezcla de productos 18, amidas conjugadas epímeras en la posición C-7a. Se ha sido estudiado la reacción de ciclocondensación de derivados de 2-oxociclohexano propionato convenientemente sustituidos en C-3 o en C-3 y C-5 con (R)-fenilglicinol y (1S,2R)-aminoindanol. Esta reacción conduce estereoselectivamente a lactamas tricíclicas o pentacíclicas quirales: se aisló mayoritariamente una lactama y se detectó la presencia de otra minoritaria. Al utilizar (1S,2R)-aminoindanol se obtuvieron mejores resultados. Estas lactamas son precursoras de cis-decahidroquinolinas, con sustituyentes en la posición 8 o en la posición 6 y 8. Las etapas clave de esta transformación son la reducción con alano y la eliminación del inductor quiral. Con esta metodología se ha preparado la decahidroquinolina 82, precursor de numerosos alcaloides de la familia Mirioneuron nutans. Además, presentamos el estudio de las reacciones de ciclocondensación con (R)-fenilglicinol a partir de ciclohexanonas que poseen una cadena de acetato en la posición C-1 y diversos sustituyentes alquilo o arilo en la posición C-3. Esta reacción conduce estereoselectivamente a una sola lactama tricíclica de las ocho posibles. A partir de las cetonas con un sustituyente alquilo en la posición C-3 aislamos una cantidad variable de enamida. Las lactamas mayoritarias, fueron convertidas en cis-octahidroindoles y cis-octahidroindolonas, que presentan un sustituyente en la posición 7 o en las posiciones 7 y 7a del anillo carbocíclico. Además, estudiamos la reactividad de las lactamas tricíclicas en medio ácido: la reacción con TiCl4 en THF, proporciona lactamas insaturadas con elevada estereoselectividad y buen rendimiento. La presencia de la función enamida, nos permitió preparar selectivamente nuevas cis y trans octahidroindolonas. Esta metodología nos permitió sintetizar el (a)-Licorano, un metabolito de la familia de las Amaryllidaceae
Connie M Hoiness - One of the best experts on this subject based on the ideXlab platform.
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cyclopropanes from Unsaturated Compounds methylene iodide and zinc copper couple
Organic Reactions, 2011Co-Authors: Howard E Simmons, Theodore L Cairns, Susan A Vladuchick, Connie M HoinessAbstract:The reaction of the organozinc reagent prepared from methylene iodide and zinc-copper couple with substituted Unsaturated Compounds has proved to be a versatile and convenient method for the synthesis of cyclopropanes. The synthesis is stereospecific with regard to the stereochemistry of the Unsaturated Compound and is usually free from serious side reactions; it can be carried out under mild conditions in diethyl and affords cyclopropanes often in good yields. This method can be easily adapted to large-scale preparations. Two useful variations of the cyclopropanation reaction have appeared which involve the same or a similar organozinc intermediate: (1) diazomethane reacts with iodide in ether to form a reagent which converts Unsaturated Compounds to cyclopropanes; (2) methlyene iodide and diethyl zinc react in ether in the presence of Unsaturated Compounds to cyclopropanes. Processes are known in which a divalent carbon fragment adds to carbon-carbon double bonds either as a free carbene or as an organometallic complex. Keywords: cyclopropanes; methylene iodide; zinc-copper couple; alkenes; zinc reagent; hydroxyalkenes; allenes; angular methylation; experimental conditions
Christian S Rondestvedt - One of the best experts on this subject based on the ideXlab platform.
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arylation of Unsaturated Compounds by diazonium salts the meerwein arylation reaction
Organic Reactions, 2011Co-Authors: Christian S RondestvedtAbstract:The arylation of olefinic Compounds by diazonium halides with a copper salt catalyst was discovered by Meerwein. The Meerwein arylation reaction proceeds best when the olefinic double bond is activated by an electron attracting group Z, such as cyano, carbonyl, or aryl. The net result is the union of the aryl group from diazonium salt with carbon atom beta to the activating group, either by substitution of a beta hydrogen atom or the addition of Ar and Cl to the double bond. The reaction is a valuable synthetic tool. This chapter is confined to reactions in which a new carbon-carbon bond is formed between the aromatic ring of a diazonium salt and aliphatic Unsaturated Compound. Keywords: arylation; Unsaturated Compounds; diazonium salts; Meerwein arylation reaction; Unsaturated component; quinones; arylation; cinnamic acid; maleic acid; side reactions; decarboxylation; experimental conditions
Howard E Simmons - One of the best experts on this subject based on the ideXlab platform.
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cyclopropanes from Unsaturated Compounds methylene iodide and zinc copper couple
Organic Reactions, 2011Co-Authors: Howard E Simmons, Theodore L Cairns, Susan A Vladuchick, Connie M HoinessAbstract:The reaction of the organozinc reagent prepared from methylene iodide and zinc-copper couple with substituted Unsaturated Compounds has proved to be a versatile and convenient method for the synthesis of cyclopropanes. The synthesis is stereospecific with regard to the stereochemistry of the Unsaturated Compound and is usually free from serious side reactions; it can be carried out under mild conditions in diethyl and affords cyclopropanes often in good yields. This method can be easily adapted to large-scale preparations. Two useful variations of the cyclopropanation reaction have appeared which involve the same or a similar organozinc intermediate: (1) diazomethane reacts with iodide in ether to form a reagent which converts Unsaturated Compounds to cyclopropanes; (2) methlyene iodide and diethyl zinc react in ether in the presence of Unsaturated Compounds to cyclopropanes. Processes are known in which a divalent carbon fragment adds to carbon-carbon double bonds either as a free carbene or as an organometallic complex. Keywords: cyclopropanes; methylene iodide; zinc-copper couple; alkenes; zinc reagent; hydroxyalkenes; allenes; angular methylation; experimental conditions
