102-04-5Relevant articles and documents
Evidence for a 1,4-dioxy diradical as an intermediate in the thermal decomposition of 3,3-dibenzyl-1,2-dioxetane
Adam, Waldemar,Heil, Markus
, p. 8807 - 8809 (1992)
The thermal decomposition of 3,3-dibenzyl-1,2-dioxetane (1) in CDCl3 and CH2Cl2 solutions afforded the expected decomposition product 1,3-diphenyl-2-propanone (2) and the novel rearrangement ketone -(benzyloxy)-3-phenyl-2-propanone (3) in ratios of (73 ± 10):(27 ± 10). A plausible mechanism for the formation of ketone 3 involves homolytic cleavage of the dioxetane peroxide bond with subsequent β cleavage of the benzyl group in the 1,4-dioxy diradical and in-cage combination of the resulting radicals. Moreover, several control experiments render a benzyl radical-induced decomposition of dioxetane 1 unlikely Thus, the ratio of 2 and 3 was found to be essentially independent of the initial dioxetane concentration, and the presence of radical scavengers did not affect the product ratio and reaction rate. With the electron-rich 1,4-dioxene, the dioxetane 1 afforded the cycloadduct cis-3,3-dibenzyl-2,5,7,10-tetraoxabicyclo[4.4.0]decane (4) as major product.
Nickel-catalyzed cyanation of aryl halides and triflates using acetonitrile: Via C-CN bond cleavage assisted by 1,4-bis(trimethylsilyl)-2,3,5,6-tetramethyl-1,4-dihydropyrazine
Ueda, Yohei,Tsujimoto, Nagataka,Yurino, Taiga,Tsurugi, Hayato,Mashima, Kazushi
, p. 994 - 999 (2019)
We developed a non-toxic cyanation reaction of various aryl halides and triflates in acetonitrile using a catalyst system of [Ni(MeCN)6](BF4)2, 1,10-phenanthroline, and 1,4-bis(trimethylsilyl)-2,3,5,6-tetramethyl-1,4-dihydropyrazine (Si-Me4-DHP). Si-Me4-DHP was found to function as a reductant for generating nickel(0) species and a silylation reagent to achieve the catalytic cyanation via C-CN bond cleavage.
Watson,Nathan,Laurie
, p. 170,173 Anm. (1935)
Synthetic Methods and Reactions; 108. Cleavage of Ethanediyl S,S-Acetals with Iodo(Bromo)trimethylsilane/Dimethyl Sulfoxide
Olah, George A.,Narang, Subbash C.,Mehrotra, Ashok K.
, p. 965 - 966 (1982)
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Carbonylative coupling of organozinc reagents in the presence and absence of aryl iodides: Synthesis of unsymmetrical and symmetrical ketones
Jackson, Richard F. W.,Turner, Debra,Block, Michael H.
, p. 865 - 870 (1997)
The utility of the palladium(o) catalysed reaction of the iodoalanine-derived organozinc reagent 6a with functionalised aryl iodides, under a carbon monoxide atmosphere, to give protected 4-aryl-4-oxo α-amino acids 8, is illustrated by a short synthesis of L-kynurenine 4. Treatment of functionalised organozinc reagents with catalytic tetrakis(triphenylphosphine)palladium(0) under an atmosphere of carbon monoxide in the absence of any electrophile leads to the formation of symmetrical functionalised ketones 9 in good yields. This reaction is illustrated by a one-step synthesis of protected (2S,6S)-4-oxo-2,6-diaminopimelic acid 9a from commercially available compounds. It has been established that adventitious molecular oxygen plays a key role in the formation of the symmetrical ketones 9, and that rigorous exclusion of oxygen can result in substantially higher yields of ketones 8 in the cross-coupling with some aromatic iodides.
ELCTROCHEMICAL PREPARATION AND REACTIONS OF UNMASKED ACYL-ANION SYNTHONS
Yoshida, Kunihisa,Kunugita, Ei-ichi,Kobayashi, Masaru,Amano, Sei-ichi
, p. 6371 - 6374 (1989)
Organic halides can be converted into carbonyl compounds by electroreducing a mixture of them and Fe(CO)5 in acetonitrile first and adding an electrophile to this mixture.
Deoximation of Oxime O-acetates, Oximes, and Oxime Ethers by Nonacarbonyldiiron or Pentacarbonyliron. An Electronic Effect for the N-O Bond Cleavage
Nitta, Makoto,Sasaki, Ichiro,Miyano, Hiroyuki,Kobayashi, Tomoshige
, p. 3357 - 3358 (1984)
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Mechanism of the nickel-catalyzed electrosynthesis of ketones by heterocoupling of acyl and benzyl halides
Amatore, Christian,Jutand, Anny,Perichon, Jacques,Rollin, Yolande
, p. 1293 - 1304 (2000)
The mechanism of the nickel-catalyzed electrosynthesis of ketones by heterocoupling of phenacyl chloride and benzyl bromide has been investigated by fast scan rate cyclic voltammetry with [Ni(bpy)2+3](BF-4)2 as the catalytic precursor (bpy = 2,2′-bipyridine). The key step is an oxidative addition of Ni0(bpy) (electrogenerated by reduction of the Ni(II) precursor) to PhCH2Br whose rate constant is found to be 10 times higher than that of PhCH2COCl. The complex PhCH2NiIIBr(bpy) formed in the oxidative addition is reduced at the potential of the NiII/Ni0 reduction by a two-electron process which affords an anionic complex PhCH2Ni0(bpy)- able to react with PhCH2COCl to generate eventually the homocoupling product PhCH2COCH2Ph. The formation of the homocoupling product PhCH2COCOCH2Ph is prevented because of the too slow oxidative addition of Ni0(bpy) to PhCH2COCl compared to PhCH2Br. The formation of the homocoupling product PhCH2CH2Ph is also prevented because PhCH2Ni0(bpy)- does not react with PhCH2Br. This explains why the electrosynthesis of the ketone can be performed selectively in a one-pot procedure, starting from an equal mixture of PhCH2COCl and PhCH2Br and a nickel catalyst ligated by the bpy ligand.
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Flood,T.C.,Sarhangi,A.
, p. 3861 - 3864 (1977)
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Synthesis of unsymmetrical ketones by applying visible-light benzophenone/nickel dual catalysis for direct benzylic acylation
Krach, Patricia E.,Dewanji, Abhishek,Yuan, Tingting,Rueping, Magnus
, p. 6082 - 6085 (2020)
Herein, we report a dual catalytic system for the direct benzylic C-H acylation reaction furnishing a variety of unsymmetrical ketones. A benzophenone-derived photosensitizer combined with a nickel catalyst has been established as the catalytic system. Both acid chlorides and anhydrides are able to acylate the benzylic position of toluene and other methylbenzenes. The method offers a valuable alternative to late transition metal catalyzed C-H acylation reactions.
Thibblin,Jencks
, p. 4963,4967 (1979)
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Bellassoued,Gaudemar
, p. 139,141 (1974)
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Nakai et al.
, p. 1003 (1959)
CONCERNING THE MECHANISM OF A CYANOMETALLATE MEDIATED CARBONYLATION REACTION
Rosario, R. del,Stuhl, L. S.
, p. 3999 - 4002 (1982)
The 2- anion (I) reacts with either one or two equivalents of benzyl bromide in either water/acetone or anhydrous acetonitrile to produce mainly 1,3-diphenyl-2-propanone.Excess carbon monoxide inhibitis the reaction.These results are interpreted as indicating that I is an intermediate in the reaction of K4 with CO and PhCH2Br to form 1,3-diphenyl-2-propanone.
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Possel,Leusen
, p. 4229,4230-4231 (1977)
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ACTIVATED METALLIC NICKEL IN PREPARATION OF SYMMETRICAL 1,3-DIARYLPROPAN-2-ONES FROM BENZYLIC HALIDES AND OXALYL CHLORIDES
Inaba, Shin-ichi,Rieke, Reuben D.
, p. 25 - 28 (1984)
Oxidative addition of benzylic halides to nickel in the metallic state followed by insertion of carbon monoxide generated from alkyl oxalyl chlorides proceeded smoothly to give symmetrical 1,3-diarylpropan-2-ones in moderate yields.
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Adkins et al.
, p. 3622,3623 (1949)
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Richardson et al.
, p. 9277 (1972)
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Electrochemical Synthesis of Symmetrical Ketones from Acid Chlorides
Folest, Jean-Claude,Pereira-Martins, Edouard,Troupel, Michel,Perichon, Jacques
, p. 7571 - 7574 (1993)
The electrochemical reduction of aroyl or arylacetyl chlorides was performed in an undivided cell fitted with a stainless steel anode and a nickel foam cathode.The electrolyses were carried out at constant current in acetonitrile as solvent, leading to the corresponding symmetrical ketones. Key words: symmetrical ketones synthesis, acid chloride electroreduction.
Fully Substituted Conjugate Benzofuran Core: Multiyne Cascade Coupling and Oxidation of Cyclopropenone
Yao, Liangliang,Hu, Qiong,Bao, Li,Zhu, Wenjing,Hu, Yimin
supporting information, p. 4971 - 4975 (2021/06/30)
An unprecedented C═C double bond cleavage of cyclopropenone and dioxygen activation by multiyne cascade coupling has been developed. This chemistry provides a novel, simple, and efficient approach to synthesize fully substituted conjugate benzofuran derivatives from simple substrates under mild conditions. The density functional theory (DFT) calculations reveal that the unique homolytic cleavages of cyclopropenone and molecular oxygen are crucial to the success of this reaction.
Cascade Ring-Opening Dual Halogenation of Cyclopropenones with Saturated Oxygen Heterocycles
Gao, Wen-Xia,Huang, Xiao-Bo,Liu, Miao-Chang,Miao, Wei-Hang,Wu, Hua-Yue,Zhou, Yun-Bing
supporting information, p. 9425 - 9430 (2021/12/14)
Represented is a CuX2- or I2-promoted ring-opening dual halogenation of cyclopropenones with saturated oxygen heterocycles, providing an efficient method for the synthesis of 3-haloacrylates. The ring-opening reaction enables the construction of two C–X (X = Cl, Br, or I) bonds and a C–O bond as well as the cleavage of two C–O bonds and a C–C bond in a single step. This protocol is highly atom economical, has an excellent substrate scope, and exhibits the ability for gram-scale reaction.
Sulfonium ion-promoted traceless Schmidt reaction of alkyl azides
Ardiansah, Bayu,Kakiuchi, Kiyomi,Morimoto, Tsumoru,Tanimoto, Hiroki,Tomohiro, Takenori
, p. 8738 - 8741 (2021/09/08)
Schmidt reaction by sulfonium ions is described. General primary, secondary, and tertiary alkyl azides were converted to the corresponding carbonyl or imine compounds without any trace of the activators. This bond scission reaction through 1,2-migration of C-H and C-C bonds was accessible to the one-pot substitution reaction.
