372-80-5Relevant academic research and scientific papers
N-Hydroxybenzimidazole as a structurally modifiable platform forN-oxyl radicals for direct C-H functionalization reactions
Hatanaka, Miho,Jiang, Julong,Maruoka, Keiji,Matsumoto, Akira,Sakamoto, Ryu,Sakurai, Shunya,Tsuzuki, Saori,Yoshii, Tomomi
, p. 5772 - 5778 (2020/06/22)
Methods for direct functionalization of C-H bonds mediated byN-oxyl radicals constitute a powerful tool in modern organic synthesis. While severalN-oxyl radicals have been developed to date, the lack of structural diversity for these species has hampered further progress in this field. Here we designed a novel class ofN-oxyl radicals based onN-hydroxybenzimidazole, and applied them to the direct C-H functionalization reactions. The flexibly modifiable features of these structures enabled facile tuning of their catalytic performance. Moreover, with these organoradicals, we have developed a metal-free approach for the synthesis of acyl fluoridesviadirect C-H fluorination of aldehydes under mild conditions.
Homogeneous catalytic hydrogenation of perfluoro methyl esters
Lazzari, Dario,Cassani, Maria Cristina,Bertola, Maurizio,Moreno, Francisco Casado,Torrente, Damiano
, p. 15582 - 15584 (2013/09/12)
The first example of perfluoroalkyl methyl ester RfC(O)OMe (Rf = C3F7, C5F11) reduction by homogeneous catalytic hydrogenation with the ruthenium catalyst Ru-MACHO is herein reported. The hydrogenation process leads to the corresponding perfluorinated alcohols thus replacing sodium borohydride that has so far represented the state of art in perfluoro ester reduction.
Oxidation of primary aliphatic and aromatic aldehydes with difluoro(aryl)-λ3-bromane
Ochiai, Masahito,Yoshimura, Akira,Hoque, Md. Mahbubul,Okubo, Takuji,Saito, Motomichi,Miyamoto, Kazunori
supporting information; experimental part, p. 5568 - 5571 (2011/12/03)
Oxidation of primary aliphatic aldehydes with p- trifluoromethylphenyl(difluoro)-λ3-bromane in dichloromethane at 0 °C afforded acid fluorides selectively in good yields, while that of aromatic aldehydes in chloroform at room temperature produced aryl difluoromethyl ethers. A larger migratory aptitude of aryl groups compared to primary alkyl groups during a 1,2-shift from carbon to an electron-deficient oxygen atom in bromane(III) Criegee-type intermediates will result in these differences in the reaction courses.
Reactions of caesium fluoroxysulphate with organic molecules part 25 1. Reactions with ethers
Stavber, Stojan,Kosir, Iztok,Zupan, Marko
, p. 183 - 186 (2007/10/03)
The reactions of caesium fluoroxysulphate in MeCN suspension at room temperature with di-benzyl, di-alkyl or benzyl-alkyl ethers resulted in oxidative cleavage of the ethers forming pairs of corresponding aldehydes and alcohols, which could be further transformed into acid fluorides under the reaction conditions used. Di-benzyl ether was thus transformed to a mixture of benzyl alcohol, benzaldehyde and benzoyl fluoride as the main products and benzyl benzoate as the a minor one, while di-n-hexyl ether resulted in a mixture of n-hexanol, hexanal, hexanoyl fluoride and hexyl hexanoate. The reaction of benzyl hexyl ether resulted in a mixture of benzaldehyde, benzoyl fluoride and hexanol as the main, and benzyl alcohol, hexanal, hexanoyl fluoride and hexyl benzoate as the minor products. A reaction mechanism including radical intermediates was proposed.
Selective Electrochemical Formyl Hydrogen-Exchange Fluorination of Aliphatic Aldehydes to Prepare Acyl Fluorides Using HF-Base Solutions
Yoneda, Norihiko,Chen, Sheng-Qi,Hatakeyama, Tsuyoshi,Hara, Syoji,Fukuhara, Tsuyoshi
, p. 849 - 850 (2007/10/02)
The selective displacement of formyl hydrogen to fluorine in aliphatic aldehydes was successfully carried out electrochemically to give acyl fluorides in base-nHF (base: pyridine or Et3N, n=3-6) electrolyte solution with or without solvents such as acetonitrile and sulfolane.
MILD CONVERSION OF PRIMARY ALCOHOLS AND ALDEHYDES TO ACID FLUORIDES WITH CAESIUM FLUOROXYSULPHATE
Stavber, Stojan,Planinsek, Zdenka,Zupan, Marko
, p. 6095 - 6096 (2007/10/02)
Caesium fluoroxysulphate in acetonitrile medium at 35 deg C converts primary alcohols and alkyl, as well as aryl aldehydes, to acid fluorides in high yield.
FLUORIERUNGSEIGENSCHAFTEN VON WF6
Haas, A.,Maciej, Th.
, p. 581 - 588 (2007/10/02)
WF6 reacts with aliphatic carbonyl- or carboxyl derivates to form the corresponding difluorides or carbonic acid fluorides.Fluorination of carbonyl compounds makes the presence of a Lewis acid like BF3 necessary.Trifluoromethyl compounds are not available in this way.Selective fluorination of alcoholes with WF6 is not possible.
Reactions of Perfluoro-2-methyl-2-pentene with Carboxylic Acids, Alcohols, and Some Cyclic Amides. A New Fluorinating Reagent
Yanagida, Shozo,Noji, Yukihiro,Okahara, Mitsuo
, p. 1151 - 1158 (2007/10/02)
Perfluoro-2-methyl-2-pentene (PMP) reacts with carboxylic acids, alcohols, and 2-pyridone, giving Michael-type addition products, 1,1,1,3,4,4,5,5,5-nonafluoro-2-trifluoromethyl-3-acyloxypentane, 1,1,1,3,4,4,5,5,5-nonafluoro-2-trifluoromethyl-3-alkoxypentane, 1,1,1,3,4,4,5,5,5-nonafluoro-2-trifluoromethyl-3(2-pyridyloxy)pentane, respectively, in good yields.In the presence of bases, carboxylic acids give acid fluorides, 1,1,1,4,4,5,5,5-octafluoro-2-trifluoromethyl-3-pentanone, and 1,1,1,4,4,5,5,5-octafluoro-2-trifluoromethyl-3-acyloxy-2-pentene (4), the yields changing with base, solvent, phase-transfer catalyst, and their combination.In the presence of triethylamine, fluorination occurs exclusively, producing acid fluorides in good yields.Alcohols and 2-pyridone are converted into alkyl fluorides and 2-fluoropyridine, respectively, with use of triethylamine as a base with an aprotic solvent.The reaction of PMP with 4-pyridone and 6-chloro-2-ethyl-5-methyl-4(3H)-pyrimidone were also examined.The fluorination reactions were rationalized by preferential replacement of the vinylic fluorine of PMP and a good leaving function of the perfluoro enol group of the intermediates such as 4.
