The Experts below are selected from a list of 309 Experts worldwide ranked by ideXlab platform
Arturo Espinosa Ferao - One of the best experts on this subject based on the ideXlab platform.
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Comparative Computational Study on the Reaction of Chloroacetone with Trimethylphosphite: Perkow versus Michaelis-Arbuzov Reaction Paths.
The journal of physical chemistry. A, 2017Co-Authors: Arturo Espinosa FeraoAbstract:Two competitive mechanistic pathways for the Reaction between trimethyl phosphite and chloroacetone are analyzed by high-level calculations. FMO analysis and HSAB-derived descriptors point to a preferential initial interaction of the nucleophile with the carbonyl group as electrophile. The Perkow Reaction starts by chelotropic addition of the P atom to the carbonyl C-O bond, which is the rate determining step in THF solution, yielding an oxaphosphirane intermediate. The oxaphosphirane undergoes sequential P-C bond cleavage with elimination of chloride ion and O-demethylation. The alternative Michaelis-Arbuzov Reaction involves nucleophilic displacement of chloride by the P atom and subsequent O-demethylation. The Perkow path is kinetically and thermodynamically favoured with respect to the Michaelis-Arbuzov path in the gas phase, but only kinetically preferred in polar (THF) solvents.
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Comparative Computational Study on the Reaction of Chloroacetone with Trimethylphosphite: Perkow versus Michaelis–Arbuzov Reaction Paths
2017Co-Authors: Arturo Espinosa FeraoAbstract:Two competitive mechanistic pathways for the Reaction between trimethyl phosphite and chloroacetone are analyzed by high-level calculations. FMO analysis and HSAB-derived descriptors point to a preferential initial interaction of the nucleophile with the carbonyl group as electrophile. The Perkow Reaction starts by chelotropic addition of the P atom to the carbonyl C–O bond, which is the rate-determining step in THF or CH2Cl2 solution, yielding an oxaphosphirane intermediate. The oxaphosphirane undergoes sequential P–C bond cleavage with elimination of chloride ion and O-demethylation. The alternative Michaelis–Arbuzov Reaction involves nucleophilic displacement of chloride by the P atom and subsequent O-demethylation. The Perkow path is kinetically and thermodynamically favored with respect to the Michaelis–Arbuzov path in the gas phase, but it is only kinetically preferred in polar (THF or CH2Cl2) solvents
Susumu Kobayashi - One of the best experts on this subject based on the ideXlab platform.
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efficient synthesis of 3 o thia cpa and preliminary analysis of its biological activity toward autotaxin
ChemInform, 2011Co-Authors: Ryo Tanaka, Masaru Kato, Takahiro Suzuki, Atsuo Nakazaki, Emi Nozaki, Mari Gotoh, Kimiko Murakamimurofushi, Susumu KobayashiAbstract:Cyclic thiophosphatidic acids of type (V) (4 examples) are prepared involving an intramolecular Arbuzov Reaction as the key step.
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efficient synthesis of 3 o thia cpa and preliminary analysis of its biological activity toward autotaxin
Bioorganic & Medicinal Chemistry Letters, 2011Co-Authors: Ryo Tanaka, Masaru Kato, Takahiro Suzuki, Atsuo Nakazaki, Emi Nozaki, Mari Gotoh, Kimiko Murakamimurofushi, Susumu KobayashiAbstract:The efficient synthesis of 3-O-thia-cPAs (4a-d), sulfur analogues of cyclic phosphatidic acid (cPA), has been achieved. The key step of the synthesis is an intramolecular Arbuzov Reaction to construct the cyclic thiophosphate moiety. The present synthetic route enables the synthesis of 4a-d in only four steps from the commercially available glycidol. Preliminary biological experiments showed that 4a-d exhibited a similar inhibitory effect on autotaxin (ATX) as original cPA.
Libiao Han - One of the best experts on this subject based on the ideXlab platform.
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alcohol based michaelis Arbuzov Reaction an efficient and environmentally benign method for c p o bond formation
Green Chemistry, 2018Co-Authors: Xu Zhang, Hongen Cao, Libiao HanAbstract:The famous Michaelis–Arbuzov Reaction is extensively used both in the laboratory and industry to manufacture tons of widely-used organophosphoryl compounds every year. However, this method and the modified Michaelis–Arbuzov Reactions developed recently still have some limitations. We now report a new alcohol-version of the Michaelis–Arbuzov Reaction that can provide an efficient and environmentally-benign method to address the problems of the known Michaelis–Arbuzov Reactions. That is, a wide range of alcohols can readily react with phosphites, phosphonites, and phosphinites to give all the three kinds of phosphoryl compounds (phosphonates, phosphinates, and phosphine oxides) using an n-Bu4NI-catalyzed efficient C–P(O) bond formation Reaction. This general method can also be easily scaled up and used for further synthetic transformations in one pot.
Charles Mioskowski - One of the best experts on this subject based on the ideXlab platform.
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synthesis of di and triphosphate ester analogs via a modified michaelis Arbuzov Reaction
Tetrahedron Letters, 1995Co-Authors: Mourad Saady, Luc Lebeau, Charles MioskowskiAbstract:Abstract For the first time, benzyl phosphites allowed the preparation of a set of polyphosphonates from chloromethyl halides via the Michaelis-Arbuzov Reaction performed under vacuum. Regioselective mono-deprotection or complete deprotection of these phosphonates provide useful building blocks for the synthesis of biological phosphate analogs.
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first use of benzyl phosphites in the michaelis Arbuzov Reaction synthesis of mono di and triphosphate analogs
Helvetica Chimica Acta, 1995Co-Authors: Mourad Saady, Luc Lebeau, Charles MioskowskiAbstract:Benzyl phosphites were used in the Micaelis-Arbuzov Reaction. Special experimental conditions allowed preparation of a set of phosphonate analogs of mono-, di-, and triphosphate. Furthermore, regioselective monodeprotection makes these molecules useful building blocks for the synthesis of analogs of polyphosphorylated compounds of biological interest (e.g. nucleotides), after removal of all phosphonate benzyl ester groups under very mild conditions and high yields.
Graham R. Evans - One of the best experts on this subject based on the ideXlab platform.
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The “thio-Arbuzov” Reaction of sulfenate esters with sulfenyl chlorides: Fate of the thiosulfinate product
Tetrahedron Letters, 1996Co-Authors: Charles Brown, Graham R. EvansAbstract:Abstract The further Reaction of thiosulfinate esters (putative products of the “Thio-Arbuzov” Reaction of sulfenate esters with sulfenyl chlorides) with sulfenyl chlorides and sulfenate esters has been studied. In the former case, sulfinyl chlorides and disulfides are formed. In the latter case sulfinate esters and disulfides are obtained.