50654-42-7Relevant articles and documents
Nucleophilic addition of α-(dimethylsilyl)nitriles to aldehydes and ketones
Jinzaki, Takaaki,Arakawa, Mitsuru,Kinoshita, Hidenori,Ichikawa, Junji,Miura, Katsukiyo
supporting information, p. 3750 - 3753 (2013/08/23)
α-Alkylated (dimethylsilyl)acetonitriles (Me2HSiCR 3R4CN) react spontaneously with aldehydes in DMSO to give β-hydroxynitriles in good to high yields. The addition to ketones is effectively promoted by using MgCl2/su
Generation of carbanions through stibine-metal and bismuthine-metal exchange reactions and its applications to precision synthesis of ω-end-functionalized polymers
Kayahara, Eiichi,Yamada, Hiroto,Yamago, Shigeru
supporting information; experimental part, p. 5272 - 5280 (2011/06/20)
Generation of carbanions from organostibines and organobismuthines through heteroatom-metal exchange reactions was examined from synthetic and mechanistic viewpoints. The exchange reaction proceeded spontaneously upon treatment with various organometallic reagents, such as alkyl lithiums, tetraalkyl zincates, and alkyl magnesium halides to afford the corresponding carbanions quantitatively. Due to the high reactivity of these heteroatom compounds, the exchange reactions took place exclusively even in the presence of various polar functional groups, which potentially react with organometallic species. The advantage of this method was exemplified by the end-group transformation of living polymers that bear these heteroatom species at the ω-polymer end, prepared by using organostibine and bismuthine-mediated living radical polymerizations. Various polymers that bear polar functional groups and acidic hydrogen-for example, poly(methyl methacrylate), poly(butyl acrylate), poly(N-isopropyl acrylamide), and poly(2-hydroxyethyl methacrylate)-could be used in the exchange reactions, and subsequent trapping with electrophiles afforded the corresponding polymers with controlled molecular weights, molecular weight distributions, and end-group functionalities. Competition experiments showed that organostibines and organobismuthines were among the most reactive heteroatom compounds towards organometallic reagents and that their high reactivity was responsible for the high chemoselectivity in the exchange reaction. All's well that ends well: The generation of carbanions from organostibine and -bismuthine compounds was achieved thorough a heteroatom-metal exchange reaction (see scheme). The highly chemoselective exchange reaction could be applied to precision synthesis of varieties of ω-end- functionalized polymers that possess a polar functional group.
One-pot nitrile aldolization/hydration operation giving β-hydroxy carboxamides
Goto, Akihiro,Naka, Hiroshi,Noyori, Ryoji,Saito, Susumu
supporting information; experimental part, p. 1740 - 1743 (2011/12/16)
Rhodium to the rescue: The formal aldol products of carboxamides (CONH 2) were obtained by using a RhI(OR) (R=H, Me) catalyst under essentially neutral pH and ambient conditions. This novel aldol strategy is based on the catalytic al
Reaction of the electrogenerated cyanomethyl anion with carbonyl compounds: A clean and safe synthesis of β-hydroxynitriles
Bianchi, Gabriele,Feroci, Marta,Rossi, Leucio
experimental part, p. 3863 - 3866 (2010/01/11)
The electrogenerated cyanomethyl anion reacts with carbonyl compounds to yield the corresponding β-hydroxymtriles in moderate to high yields. The reported methodology is very clean and safe, avoiding the use of any classical base or catalyst.
RhI-catalyzed aldol-type reaction of organonitriles under mild conditions
Goto, Akihiro,Endo, Kohei,Ukai, Yu,Irle, Stephan,Saito, Susumu
, p. 2212 - 2214 (2008/12/22)
An aldol-type reaction of organonitriles with aldehydes was catalyzed by a RhI(OR) species under ambient conditions, and the reaction displayed a broad substrate scope with respect to both organonitrile and aldehyde components. The Royal Societ
Key role of Ti(IV) in the selective radical - radical cross-coupling mediated by the ingold-Fischer effect
Spaccini, Raffaele,Pastori, Nadia,Clerici, Angelo,Punta, Carlo,Porta, Ombretta
supporting information; experimental part, p. 18018 - 18024 (2009/06/28)
We report an innovative approach for the selective synthesis of polyfunctional derivatives by cross-combination of different radicals generated under mild conditions. The coordinating effect of Ti(IV) plays a key role in the reaction mechanism: due to its chelating action on the hydroxyl groups, it promotes the homolytic C-C bond cleavage of α,β-dihydroxy ketones by enhancing the captodative effect and the consequent stabilization of the corresponding α-hydroxy-α-carbonyl radicals. When these radicals are generated in the presence of stoichiometric amounts of TiCl4 and 2,2'-azo-bis-isobutyronitrile (AIBN) is employed as a source of α-cyanoisopropyl radicals, the selective radical-radical cross-coupling is observed, affording the corresponding β-hydroxynitriles in high yields. This innovative methodology allows application of the well-known Ingold-Fischer effect to a wider range of stabilized carbon-centered radicals, whose formation derives from the chelating action of Ti(IV).
Lewis base-catalyzed cyanomethylation of carbonyl compounds with (trimethylsilyl)acetonitrile
Kawano, Yoshikazu,Kaneko, Nobuya,Mukaiyama, Teruaki
, p. 1508 - 1509 (2007/10/03)
Catalytic cyanomethylation of various carbonyl compounds with (trimethylsilyl)acetonitrile (TMSCH2CN) in the presence of Lewis bases such as cesium or lithium acetate proceeded smoothly to afford the corresponding cyanomethylated adducts in good yields. Copyright
Carbopalladation of nitriles: Synthesis of benzocyclic ketones and cyclopentenones via Pd-catalyzed cyclization of ω-(2-iodoaryl)alkanenitriles and related compounds
Pletnev, Alexandre A.,Larock, Richard C.
, p. 9428 - 9438 (2007/10/03)
An efficient procedure for the synthesis of 2,2-disubstituted benzocyclic ketones by intramolecular carbopalladation of nitriles has been developed. The cyclization of substituted 3-(2-iodoaryl)-propanenitriles affords indanones in high yields. The reaction is compatible with a wide variety of functional groups. This methodology has been extended to the synthesis of tetralones and cyclopentenones.
Synthesis of benzocyclic ketones via palladium-catalyzed cyclization of ω-(2-iodoaryl)alkanenitriles
Pletnev, Alexandre A.,Larock, Richard C.
, p. 2133 - 2136 (2007/10/03)
An efficient procedure for the synthesis of 2,2-disubstituted benzocyclic ketones by intramolecular carbopalladation of nitriles has been developed. The cyclization of substituted 3-(2-iodoaryl)propanenitriles affords indanones in high yields. The reactio
Solvent dependent photochemical reactions of 3-(2-alkylphenyl)-2,2- dimethyl-3-oxopropanoates and their related compounds
Saito, Masaichi,Kamei, Yumiko,Kuribara, Kanae,Yoshioka, Michikazu,Hasegawa, Tadashi
, p. 9013 - 9018 (2007/10/03)
Photochemical reactions of methyl 3-(o-alkylphenyl)-2,2-dimethyl-3- oxopropanoates in hexane gave only the corresponding benzocyclobutenols. However, when irradiation was carried out in methanol, 3-oxonaphthalenones were produced together with the benzocyclobutenols. The ratio of benzocyclobutenol to naphthalenone depends on the bulkiness of the alkyl group in the ortho position. Intermediary 1,4-diradicals or dienols were efficiently trapped by oxygen to afford the corresponding peroxides and/or oxygenated compounds derived from the peroxides.