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Research paper thumbnail of E você, como passa pelas mudanças da sua vida

A short text about a way changing process can be seen. In Brazilian Portuguese.

Papers by Benjamin Ganchegui

Research paper thumbnail of On the biocatalytic cleavage of silicon–oxygen bonds: A substrate structural approach to investigating the cleavage of protecting group silyl ethers by serine-triad hydrolases

Journal of Molecular Catalysis B Enzymatic, 2009

The biotransformation of compounds containing silicon has recently been a subject of much interes... more The biotransformation of compounds containing silicon has recently been a subject of much interest. In this study, a variety of commercially available serine hydrolases were tested for their ability to catalyse the hydrolysis of the silicon-ether bond in a variety of silyl ethers. The hydrolysis of trimethylethoxysilane in buffer was not found to be accelerated by the presence of trypsin, chymotrypsin, or a variety of other lipase and protease enzymes. Cleavage of a range of alternative silyl ether substrates, including a trimethylsilyl (TMS) ether, by these hydrolases was also not observed, but, interestingly, only two of the enzymes tested were able to cleave a t-butyl ␣,␣,␣-carboxylate that was approximately isosteric with the TMS-protected substrate. This suggests that the cleavage of Si-O bonds by serine hydrolases, such as the cathepsin homolog silicatein-␣, may be in part limited by steric effects, as the reactive centre in the substrate is always, by analogy to C-centred substrates, tertiary, and thus inherently sterically demanding regardless of the putative catalytic competence of the enzymes.

Research paper thumbnail of Combining Chemical and Enzymatic Catalysis for the Enantioselective Oxidation of Sulfides

Research paper thumbnail of ChemInform Abstract: Palladium-Catalyzed Dehydrogenation of Benzylic Alcohols in Molten Ammonium Salts, a Recyclable System

Research paper thumbnail of ChemInform Abstract: Unusual Cleavage of the Enolsilane C-O Bond: Transformation of 2-Silyloxy-1,3-dienes into 1,3-Dienyl-2-zirconium Compounds and Their Cross-Coupling Reactions

ChemInform, 2001

reactions of organo-metal compounds reactions of organo-metal compounds O 0350 17 -077

Research paper thumbnail of ChemInform Abstract: Heck Arylation of Allylic Alcohols in Molten Salts

Research paper thumbnail of Palladium-catalyzed dehydrogenation of benzylic alcohols in molten ammonium salts, a recyclable system

Tetrahedron Letters, 2002

Heating secondary benzylic alcohols in molten tetra-n-butyl ammonium bromide with catalytic amoun... more Heating secondary benzylic alcohols in molten tetra-n-butyl ammonium bromide with catalytic amounts of palladium chloride under a gentle flow of argon produced corresponding ketones in good yields. Neither cooxidant nor additive were required, with the added advantage of catalyst and ammonium salt recycling. The dehydrogenation of primary benzylic alcohols was less selective. Such a reaction was ineffective from allylic and saturated alcohols.

Research paper thumbnail of Chiral 2-(2-Diphenylphosphinophenyl)-oxazolines: Synthesis and Use in Pd-Catalyzed Asymmetric Allylic Alkylation

Phosphorus, Sulfur, and Silicon and the Related Elements, 2006

ABSTRACT

Research paper thumbnail of Palladium nanoparticles obtained from palladium salts and tributylamine in molten tetrabutylammonium bromide: their use for hydrogenolysis-free hydrogenation of olefins

New Journal of Chemistry, 2004

Carbon-carbon double bonds have been selectively hydrogenated at room temperature in the presence... more Carbon-carbon double bonds have been selectively hydrogenated at room temperature in the presence of benzyloxy groups using an atmospheric pressure of hydrogen, toluene or [bmim]PF 6 as the solvent and palladium nanoparticles stabilized with tetrabutylammonium bromide. The system [bmim]PF 6 /palladium nanoparticles can be recycled without noticeable decrease of activity.

Research paper thumbnail of Heck arylation of allylic alcohols in molten salts

Journal of Organometallic Chemistry, 2001

The Heck coupling of ArX (X =I, Br) with allylic alcohols, carried out at 80 -120°C in molten n-B... more The Heck coupling of ArX (X =I, Br) with allylic alcohols, carried out at 80 -120°C in molten n-Bu 4 NBr using NaHCO 3 as base and PdCl 2 as catalyst without extra ligands, leads to the corresponding b-arylated carbonyl compounds. After extraction of the organic materials with diethyl ether, the ionic layer can be reused directly.

Research paper thumbnail of A new catalytic method for the synthesis of selectively substituted biphenyls containing an oxoalkyl chain

Journal of Organometallic Chemistry, 2003

A novel reaction sequence leading to the synthesis of substituted biphenyls containing a carbonyl... more A novel reaction sequence leading to the synthesis of substituted biphenyls containing a carbonyl group in an aliphatic chain has been achieved in one-pot reaction starting from iodoarenes and allylic alcohols under the catalytic action of palladium and norbornene. The latter is temporarily incorporated into a palladacycle, which directs the reaction towards the selective formation of an aryl Ã/aryl bond. Norbornene spontaneously deinserts to allow the biphenylylpalladium bond thus formed to react in its turn with the allylic alcohol. #

Research paper thumbnail of On the biocatalytic cleavage of silicon–oxygen bonds: A substrate structural approach to investigating the cleavage of protecting group silyl ethers by serine-triad hydrolases

Journal of Molecular Catalysis B: Enzymatic, 2009

The biotransformation of compounds containing silicon has recently been a subject of much interes... more The biotransformation of compounds containing silicon has recently been a subject of much interest. In this study, a variety of commercially available serine hydrolases were tested for their ability to catalyse the hydrolysis of the silicon-ether bond in a variety of silyl ethers. The hydrolysis of trimethylethoxysilane in buffer was not found to be accelerated by the presence of trypsin, chymotrypsin, or a variety of other lipase and protease enzymes. Cleavage of a range of alternative silyl ether substrates, including a trimethylsilyl (TMS) ether, by these hydrolases was also not observed, but, interestingly, only two of the enzymes tested were able to cleave a t-butyl ␣,␣,␣-carboxylate that was approximately isosteric with the TMS-protected substrate. This suggests that the cleavage of Si-O bonds by serine hydrolases, such as the cathepsin homolog silicatein-␣, may be in part limited by steric effects, as the reactive centre in the substrate is always, by analogy to C-centred substrates, tertiary, and thus inherently sterically demanding regardless of the putative catalytic competence of the enzymes.

Research paper thumbnail of Palladium-catalyzed isomerization of (homo-)allylic alcohols in molten tetrabutylammonium bromide, a recyclable system

Journal of Molecular Catalysis A: Chemical, 2004

Saturated ketones have been produced by heating secondary allylic alcohols and catalytic amounts ... more Saturated ketones have been produced by heating secondary allylic alcohols and catalytic amounts of PdCl2 or Pd(OAc)2 in molten n-Bu4NBr. After extraction of the organic material with diethyl ether, the ionic layer and the catalyst can be reused directly. Linear secondary homoallylic alcohols led also to the corresponding saturated ketones as main products. The procedure was less selective for primary

Research paper thumbnail of Heck-type reactions of allylic alcohols

Journal of Molecular Catalysis A: Chemical, 2008

Various conditions have been tested to obtain efficiently 2-methyl-1-indanone via the Pd-catalyze... more Various conditions have been tested to obtain efficiently 2-methyl-1-indanone via the Pd-catalyzed 5-endo-trig cyclization of 1-(o-bromophenyl)-2-methylprop-2-en-1-ol. High yield (97%) was obtained at 120 • C in DMF with Pd(OAc) 2 /cinchonine as the catalytic system and NaHCO 3 as the base. Use of this procedure for the synthesis of other substituted indanones led to lower yields but replacing thermal heating by microwave heating improved greatly the results.

Research paper thumbnail of Oxybromination of phenol and aniline derivatives in H2O/scCO2 biphasic media

Green Chemistry, 2007

... Process Res. Dev., 2000, 4, 270 ; N. Narender, KVV Krishna Mohan, R. Vinod Reddy, P. Srinivas... more ... Process Res. Dev., 2000, 4, 270 ; N. Narender, KVV Krishna Mohan, R. Vinod Reddy, P. Srinivasu, SJ Kulkrani and KV Ragavan, J. Mol. Catal. ... 8, KVV Krishna Mohan, N. Narender, P. Srinivasu, SJ Kulkarni and KV Rhagavan, Synth. Commun., 2004, 34, 2143 Article . ...

Research paper thumbnail of Selective aerobic oxidation in supercritical carbon dioxide catalyzed by the H5PV2Mo10O40 polyoxometalate

Chemical Communications, 2006

Research paper thumbnail of E você, como passa pelas mudanças da sua vida

A short text about a way changing process can be seen. In Brazilian Portuguese.

Research paper thumbnail of On the biocatalytic cleavage of silicon–oxygen bonds: A substrate structural approach to investigating the cleavage of protecting group silyl ethers by serine-triad hydrolases

Journal of Molecular Catalysis B Enzymatic, 2009

The biotransformation of compounds containing silicon has recently been a subject of much interes... more The biotransformation of compounds containing silicon has recently been a subject of much interest. In this study, a variety of commercially available serine hydrolases were tested for their ability to catalyse the hydrolysis of the silicon-ether bond in a variety of silyl ethers. The hydrolysis of trimethylethoxysilane in buffer was not found to be accelerated by the presence of trypsin, chymotrypsin, or a variety of other lipase and protease enzymes. Cleavage of a range of alternative silyl ether substrates, including a trimethylsilyl (TMS) ether, by these hydrolases was also not observed, but, interestingly, only two of the enzymes tested were able to cleave a t-butyl ␣,␣,␣-carboxylate that was approximately isosteric with the TMS-protected substrate. This suggests that the cleavage of Si-O bonds by serine hydrolases, such as the cathepsin homolog silicatein-␣, may be in part limited by steric effects, as the reactive centre in the substrate is always, by analogy to C-centred substrates, tertiary, and thus inherently sterically demanding regardless of the putative catalytic competence of the enzymes.

Research paper thumbnail of Combining Chemical and Enzymatic Catalysis for the Enantioselective Oxidation of Sulfides

Research paper thumbnail of ChemInform Abstract: Palladium-Catalyzed Dehydrogenation of Benzylic Alcohols in Molten Ammonium Salts, a Recyclable System

Research paper thumbnail of ChemInform Abstract: Unusual Cleavage of the Enolsilane C-O Bond: Transformation of 2-Silyloxy-1,3-dienes into 1,3-Dienyl-2-zirconium Compounds and Their Cross-Coupling Reactions

ChemInform, 2001

reactions of organo-metal compounds reactions of organo-metal compounds O 0350 17 -077

Research paper thumbnail of ChemInform Abstract: Heck Arylation of Allylic Alcohols in Molten Salts

Research paper thumbnail of Palladium-catalyzed dehydrogenation of benzylic alcohols in molten ammonium salts, a recyclable system

Tetrahedron Letters, 2002

Heating secondary benzylic alcohols in molten tetra-n-butyl ammonium bromide with catalytic amoun... more Heating secondary benzylic alcohols in molten tetra-n-butyl ammonium bromide with catalytic amounts of palladium chloride under a gentle flow of argon produced corresponding ketones in good yields. Neither cooxidant nor additive were required, with the added advantage of catalyst and ammonium salt recycling. The dehydrogenation of primary benzylic alcohols was less selective. Such a reaction was ineffective from allylic and saturated alcohols.

Research paper thumbnail of Chiral 2-(2-Diphenylphosphinophenyl)-oxazolines: Synthesis and Use in Pd-Catalyzed Asymmetric Allylic Alkylation

Phosphorus, Sulfur, and Silicon and the Related Elements, 2006

ABSTRACT

Research paper thumbnail of Palladium nanoparticles obtained from palladium salts and tributylamine in molten tetrabutylammonium bromide: their use for hydrogenolysis-free hydrogenation of olefins

New Journal of Chemistry, 2004

Carbon-carbon double bonds have been selectively hydrogenated at room temperature in the presence... more Carbon-carbon double bonds have been selectively hydrogenated at room temperature in the presence of benzyloxy groups using an atmospheric pressure of hydrogen, toluene or [bmim]PF 6 as the solvent and palladium nanoparticles stabilized with tetrabutylammonium bromide. The system [bmim]PF 6 /palladium nanoparticles can be recycled without noticeable decrease of activity.

Research paper thumbnail of Heck arylation of allylic alcohols in molten salts

Journal of Organometallic Chemistry, 2001

The Heck coupling of ArX (X =I, Br) with allylic alcohols, carried out at 80 -120°C in molten n-B... more The Heck coupling of ArX (X =I, Br) with allylic alcohols, carried out at 80 -120°C in molten n-Bu 4 NBr using NaHCO 3 as base and PdCl 2 as catalyst without extra ligands, leads to the corresponding b-arylated carbonyl compounds. After extraction of the organic materials with diethyl ether, the ionic layer can be reused directly.

Research paper thumbnail of A new catalytic method for the synthesis of selectively substituted biphenyls containing an oxoalkyl chain

Journal of Organometallic Chemistry, 2003

A novel reaction sequence leading to the synthesis of substituted biphenyls containing a carbonyl... more A novel reaction sequence leading to the synthesis of substituted biphenyls containing a carbonyl group in an aliphatic chain has been achieved in one-pot reaction starting from iodoarenes and allylic alcohols under the catalytic action of palladium and norbornene. The latter is temporarily incorporated into a palladacycle, which directs the reaction towards the selective formation of an aryl Ã/aryl bond. Norbornene spontaneously deinserts to allow the biphenylylpalladium bond thus formed to react in its turn with the allylic alcohol. #

Research paper thumbnail of On the biocatalytic cleavage of silicon–oxygen bonds: A substrate structural approach to investigating the cleavage of protecting group silyl ethers by serine-triad hydrolases

Journal of Molecular Catalysis B: Enzymatic, 2009

The biotransformation of compounds containing silicon has recently been a subject of much interes... more The biotransformation of compounds containing silicon has recently been a subject of much interest. In this study, a variety of commercially available serine hydrolases were tested for their ability to catalyse the hydrolysis of the silicon-ether bond in a variety of silyl ethers. The hydrolysis of trimethylethoxysilane in buffer was not found to be accelerated by the presence of trypsin, chymotrypsin, or a variety of other lipase and protease enzymes. Cleavage of a range of alternative silyl ether substrates, including a trimethylsilyl (TMS) ether, by these hydrolases was also not observed, but, interestingly, only two of the enzymes tested were able to cleave a t-butyl ␣,␣,␣-carboxylate that was approximately isosteric with the TMS-protected substrate. This suggests that the cleavage of Si-O bonds by serine hydrolases, such as the cathepsin homolog silicatein-␣, may be in part limited by steric effects, as the reactive centre in the substrate is always, by analogy to C-centred substrates, tertiary, and thus inherently sterically demanding regardless of the putative catalytic competence of the enzymes.

Research paper thumbnail of Palladium-catalyzed isomerization of (homo-)allylic alcohols in molten tetrabutylammonium bromide, a recyclable system

Journal of Molecular Catalysis A: Chemical, 2004

Saturated ketones have been produced by heating secondary allylic alcohols and catalytic amounts ... more Saturated ketones have been produced by heating secondary allylic alcohols and catalytic amounts of PdCl2 or Pd(OAc)2 in molten n-Bu4NBr. After extraction of the organic material with diethyl ether, the ionic layer and the catalyst can be reused directly. Linear secondary homoallylic alcohols led also to the corresponding saturated ketones as main products. The procedure was less selective for primary

Research paper thumbnail of Heck-type reactions of allylic alcohols

Journal of Molecular Catalysis A: Chemical, 2008

Various conditions have been tested to obtain efficiently 2-methyl-1-indanone via the Pd-catalyze... more Various conditions have been tested to obtain efficiently 2-methyl-1-indanone via the Pd-catalyzed 5-endo-trig cyclization of 1-(o-bromophenyl)-2-methylprop-2-en-1-ol. High yield (97%) was obtained at 120 • C in DMF with Pd(OAc) 2 /cinchonine as the catalytic system and NaHCO 3 as the base. Use of this procedure for the synthesis of other substituted indanones led to lower yields but replacing thermal heating by microwave heating improved greatly the results.

Research paper thumbnail of Oxybromination of phenol and aniline derivatives in H2O/scCO2 biphasic media

Green Chemistry, 2007

... Process Res. Dev., 2000, 4, 270 ; N. Narender, KVV Krishna Mohan, R. Vinod Reddy, P. Srinivas... more ... Process Res. Dev., 2000, 4, 270 ; N. Narender, KVV Krishna Mohan, R. Vinod Reddy, P. Srinivasu, SJ Kulkrani and KV Ragavan, J. Mol. Catal. ... 8, KVV Krishna Mohan, N. Narender, P. Srinivasu, SJ Kulkarni and KV Rhagavan, Synth. Commun., 2004, 34, 2143 Article . ...

Research paper thumbnail of Selective aerobic oxidation in supercritical carbon dioxide catalyzed by the H5PV2Mo10O40 polyoxometalate

Chemical Communications, 2006