- C-H and C-C bond activation of primary amines through dehydrogenation and transimination
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Matrix presented Dehydrogenation and subsequent transimination of primary amines offer a new pathway for C-H bond activation, ortho-alkylation, and C-C bond activation to afford a variety of ketones in the reaction of 1-alkene by a cocatalyt system of Rh(I) and 2-amino-3-picoline.
- Jun, Chul-Ho,Chung, Kwan-Yong,Hong, Jun-Bae
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- Long-Range Self-Assembly of an Electron-Deficient Hexaazatrinaphthylene with Out-of-Plane Substituents
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The unprecedented time-dependent long-range supramol-ecular assembly of electron-deficient hexaazatrinaphthylene (HATN) core based on peripheral crowding with three out-of-plane cyclic ketals is reported. The single-crystal X-ray structure of the diethyl derivative provided detailed information as to how four molecules in a repeating unit were packed in order to avoid steric crowding of the out-of-plane cyclic ketal side chain, providing locking and fastening for stabilizing the self-assembled structure. The polarizing optical microscopy (POM) and differential scanning calorimetry (DSC) did not instantaneously show any phase transition upon the cooling process. To our surprise, POM images showed a nucleation of spherulite up to 100 μm after 24 hour later. X-ray diffraction data further confirmed that these soft crystal formed a hexagonal-like crystal. The long-range self-assembly of the new material showed a slight red shift in the UV-vis absorption spectra and further substantiated by computational method.
- Chen, Yi-Ru,Zhang, Yong-Yun,Yeh, Ming-Che,Luo, Ying-Ting,Ong, Chi Wi
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- Synthesis of symmetrical ketones from Grignard reagents and 1,1′-carbonyldiimidazole
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Coupling reactions of 1,1′-carbonyldiimidazole with Grignard reagents provide a rapid and straightforward method for the synthesis of symmetrical ketones. Georg Thieme Verlag Stuttgart.
- Bottalico, Daniela,Fiandanese, Vito,Marchese, Giuseppe,Punzi, Angela
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experimental part
p. 2316 - 2318
(2010/02/28)
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- Catalytic activation of C-H and C-C bonds of allylamines via olefin isomerization by transition metal complexes
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(matrix presented) The metal-catalyzed reaction of olefins with allylamines bearing coordination sites (2-pyridyl groups) was studied. With Ru3(CO)12 as catalyst, activation of C-H bonds led to the formation of ketimines that were hydrolyzed to give asymmetric ketones. With [(C8H14)2RhCl]2, both C-H and C-C bonds were activated and symmetric ketones were formed on hydrolysis. The reaction involves double bond migration of the allylamine to form an aldimine.
- Jun, Chul-Ho,Lee, Hyuk,Park, Jae-Bum,Lee, Dae-Yon
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p. 2161 - 2164
(2008/02/11)
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- The CoCl2/Ph(Et)2N:BH3/CO system: Reactions of the borane and cobalt carbonyl species
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The CoCl2/Ph(Et)2N:BH3/CO system is useful for the hydroboration and carbonylation of alkenes to obtain the corresponding dialkyl ketones. The cobalt carbonyl species formed in situ in this way is also useful for hydroacylation-cyclisation of norbornene and for the Pauson-Khand reaction.
- Rao, M. Lakshmi Narayana,Periasamy, Mariappan
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- Synthesis of Dialkyl Ketones from Alkenes Using Ph(Et)2N:BH3/CoCl2/CO Reagent System
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Reaction of alkenes with Ph(Et)2N:BH3/CoCl2/Co in THF followed by oxidation gives the corresponding dialkyl ketones.
- Rao, Maddali L. N.,Periasamy, Mariappan
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p. 9069 - 9070
(2007/10/02)
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- Convenient method for the preparation of catecholborane and promotion of the formation of alkenyl catecholborane using BH3 complexes
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Catecholborane is prepared in benzene by passing B2H6, generated from I2/NaBH4, through a suspension of catechol at 25 deg C.The reagent prepared in this way is used for hydroboration-oxidation of representative alkenes and alkynes at 80 deg C.Hydroboration of 1-alkynes followed by iodination with I2/NaOH gives the corresponding trans-1-alkenyl iodides in 70-72percent yield.The alkenyl catecholboranes can be prepared at 25 deg C by performing the reaction in the presence of 10 molepercent of H3B:N(C2H5)2Ph or H3B:THF.The reaction is believed to go through hydroboration of thealkynes by borane followed by exchange with catecholborane.Studies of the preparation of dialkylphenoxyboranes and alkenyldiphenoxyboranes through hydroboration of 1-decene and 1-decyne by use of H3B:N(C2H5)2Ph and phenol are also reported.
- Suseela, Y.,Periasamy, M.
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- Carbonylation of R2BI in the presence of NaCo(CO)4 and Na2Fe(CO)4: A simple synthesis of dialkyl ketones
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Reaction of NaCo(CO)4 with R2BI under carbon monoxide at atmospheric pressure at room temperature readily gives the dialkyl ketones in good yields (61-85 percent) after H2O2/OH- oxidation.
- Devasagayaraj, A.,Rao, Narayana M. Lakshmi,Periasamy, M.
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p. 147 - 150
(2007/10/02)
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- Electrosynthesis of symmetrical ketones from organic halides and carbon dioxide catalysed by 2,2'-bipyridine-nickel complexes
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The electrochemical reduction of 1 2,2'-bipyridine-nickel complex, in the presence of carbon dioxide in N-methylpyrrolidone or dimethylformamide as solvent gives the corresponding nickel(0) complex associated with two molecules of CO.Oxidative addition of an alkyl halide to this complex, followed by an internal CO shift and reductive elimination, leads to the formation of a symmetrical ketone in high yield along with nickel(II), whereas aryl or vinyl halides mainly give acyl derivatives.The nickel(0) species is electrochemically regenerated, thus giving rise to an efficient catalytic process.The possible mechanism of these reactions is discussed
- Garnier, L.,Rollin, Y.,Perichon, J.
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p. 347 - 358
(2007/10/02)
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- A SIMPLE SYNTHESIS OF DIALKYLKETONES FROM ALKENES VIA HYDROBORATION-CARBENOIDATION
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Hydroboration of alkenes with sodium acetoxyborohydride (NaBH3OAc) followed by carbenoidation using NaoCH3/CHCl3 sytem and oxidation with H2O2/NaOH give dialkylketones.
- Narayana, C.,Periasamy, M.
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p. 6361 - 6364
(2007/10/02)
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- ACETOXYBOROHYDRIDE: A SIMPLE SELECTIVE HYDROBORATING AGENT
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Acetoxyborohydride (CH3COOBH3) hydroborates olefins in the presence of some reducible functional groups.
- Narayana, C.,Periasamy, M.
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p. 1757 - 1760
(2007/10/02)
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- Lithiation of Alkoxyalkyl Phenyl Sulfones. New Approach to Acyl Anion Synthesis
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(1-Ethoxyethoxy)methyl and (1-ethoxyethoxy)ethyl phenyl sulfones undergo metalation with LDA in THF in the presence of HMPA.The resulting lithium salts were easily alkylated with various alkyl halides and hydrolyzed under mild conditions to give the corresponding carbonyl compounds.The new synthetic method for the preparation of aldehydes and ketones employing these carbanions has been developed.
- Tanaka, Kazuhiko,Matsui, Syuichi,Kaji, Aritsune
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p. 3619 - 3622
(2007/10/02)
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