133127-73-8Relevant articles and documents
Development of an anodic substitution reaction system using acoustic emulsification
Asami, Ryosuke,Fuchigami, Toshio,Atobe, Mahito
, p. 244 - 246 (2008)
The anodic substitution reaction proceeded smoothly without affecting the oxidation of the nucleophile in a one-step electrochemical operation using acoustic emulsification. The Royal Society of Chemistry.
Electroorganic chemistry. 99. β-Acetoxylation and β-halogenation of N-methoxycarbonyl cyclic amines
Shono, Tatsuya,Matsumura, Yoshihiro,Onomura, Osamu,Ogaki, Masaru,Kanazawa, Takenobu
, p. 536 - 541 (1987)
Anodic oxidation of N-(methoxycarbonyl)pyrrolidines (n = 1) and -piperidines (n = 2) (A) gave α,β-disubstituted compounds B, in which the α-substituent was an acetoxy, hydroxy, or methoxy group and the β-substituent was an acetoxy group or halogen atom. The α-substituents of B were easily removed by NaBH4 under acidic conditions to give β-substituted compounds C. A reaction mechanism involving the formation of α,β-unsaturated intermediate E followed by anodic oxidation of E or attack of halogen-active species on E has been presented for the anodic α,β-disubstitution.
A new approach to anodic substitution reaction using acoustic emulsification
Asami, Ryosuke,Fuchigami, Toshio,Atobe, Mahito
, p. 1938 - 1943 (2008)
We have developed a novel electrolytic system for anodic substitution reactions using acoustic emulsification. This new system involves the generation of a carbocation by anodic oxidation of a substrate, and then its reaction with a nucleophile droplet formed by ultrasonication. In this system, even if the oxidation potential of the nucleophile is lower than that of the substrate, the substrate was predominantly oxidized to give the corresponding cation intermediate because the nucleophile phase, which was insoluble in the electrolytic medium, was electro-inactive. In addition, the overoxidation of the desired products was considerably suppressed by the extraction of products from the electrolyte solution into the nucleophile phase. As a result, the anodic substitution reaction of several carbamates with allyltrimethylsilane was carried out to provide the corresponding products in good to moderate yields. The Royal Society of Chemistry.
A novel electrosynthetic system for anodic substitution reactions by using parallel laminar flow in a microflow reactor
Horii, Daisuke,Amemiya, Fumihiro,Fuchigami, Toshio,Atobe, Mahito
, p. 10382 - 10387 (2008)
We have developed a novel electrosynthetic system for anodic substitution reactions by using parallel laminar flow in a microflow reactor. This system enables nucleophilic reactions to overcome the restraint, such as the oxidation potential of nucleophiles and the stability of cationic intermediates, by the combined use of ionic liquids as reaction media and the parallel laminar flow in the microflow reactor. By using this novel electrosynthetic system, the anodic substitution reaction of carbamates, especially of cyclic carbamates, with allyltrimethylsilane were carried out to provide the corresponding products in moderate to good conversion yields in a single flow-through operation at ambient temperature (without the need for low-temperature conditions).
Electrochemical deallylation of α-allyl cyclic amines and synthesis of optically active quaternary cyclic amino acids
Kirira, Peter G.,Kuriyama, Masami,Onomura, Osamu
experimental part, p. 3970 - 3982 (2010/07/04)
Electrochemical oxidation of α-allylated and α-betizylated N-acylated cyclic amines by using a graphite anode easily affords the corresponding α-methoxylated products with up to 76% yield. Ease of oxidation was affected by the type of electrode, the size
Synthesis of alkaloid analogues from β-amino alcohols by β-fragmentation of primary alkoxyl radicals
Boto, Alicia,Hernandez, Dacil,Hernandez, Rosendo,Montoya, Adriana,Suarez, Ernesto
, p. 325 - 334 (2007/10/03)
The fragmentation of primary alkoxyl radicals is usually a minor process with respect to hydrogen abstraction and other competing reactions. However, when β-amino alcohols were used as substrates, the scission proceeded in good to excellent yields and no side reactions were observed. The fragmentation can be coupled with an allylation or alkylation reaction, to give alkaloid analogues and functionalized nitrogen heterocycles. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.
Enzymatic resolution of cyclic N-Boc protected β-aminoacids
Pousset, Cyrille,Callens, Roland,Haddad, Mansour,Larcheveque, Marc
, p. 3407 - 3412 (2007/10/03)
Methyl and ethyl esters of N-Boc homoproline, homopipecolic acid and 3-carboxymethyl-morpholine were kinetically resolved by hydrolysis catalysed by Burkholderia cepacia lipase to give the corresponding acids and residual esters in enantiomeric excesses better than 99% (E > 100).
Synthesis of alkaloids from aminol derivatives by β-fragmentation of primary alkoxyl radicals
Boto, Alicia,Hernández, Rosendo,Montoya, Adriana,Suárez, Ernesto
, p. 1559 - 1563 (2007/10/03)
The fragmentation of primary alkoxyl radicals, often described as low yielding and plagued by side reactions, proceeded in good to excellent yields when aminol derivatives were used as substrates. Remarkably, no side reactions such as hydrogen abstraction
Synthesis of alkaloids from amino acids via N-acyliminium ions generated by one-pot radical decarboxylation-oxidation
Boto, Alicia,Hernández, Rosendo,Suárez, Ernesto
, p. 2899 - 2902 (2007/10/03)
A one-pot methodology for the synthesis of α-substituted nitrogen heterocycles from commercial amino acids has been developed. Good stereoselectivity can be achieved with chiral substituted rings. This procedure has been applied to the synthesis of piperidine, pyrrolidine and indolizidinone alkaloids. (C) 2000 Elsevier Science Ltd.
Direct oxidative carbon-carbon bond formation using the cation pool method. 1. Generation of iminium cation pools and their reaction with carbon nucleophiles
Yoshida, Jun-ichi,Suga, Seiji,Suzuki, Shinkiti,Kinomura, Naoya,Yamamoto, Atsushi,Fujiwara, Kazuyuki
, p. 9546 - 9549 (2007/10/03)
We have developed a method that involves the generation of a cation pool using low-temperature electrolysis, and then its reaction with nucleophiles under non-oxidative conditions. This one-pot method solves problems associated with conventional oxidative generation of cations and their in situ reaction with nucleophiles, and provides an efficient method for direct oxidative carbon-carbon bond formation. As an example of this method, generation of cation pools from carbamates by low-temperature electrolysis (-72°C) and their reactions with carbon nucleophiles such as allylsilanes, enol silyl ethers, and enol acetates were examined and the desired products were obtained in good yields. Aromatic compounds and 1,3-dicarbonyl compounds can also be utilized as carbon nucleophiles. The present method was also applied to combinatorial parallel synthesis using a robotic synthesizer.
