51122-91-9Relevant articles and documents
Photocatalytic Hydromethylation and Hydroalkylation of Olefins Enabled by Titanium Dioxide Mediated Decarboxylation
Zhu, Qilei,Nocera, Daniel G.
supporting information, p. 17913 - 17918 (2020/12/04)
A versatile method for the hydromethylation and hydroalkylation of alkenes at room temperature is achieved by using the photooxidative redox capacity of the valence band of anatase titanium dioxide (TiO2). Mechanistic studies support a radical-based mechanism involving the photoexcitation of TiO2 with 390 nm light in the presence of acetic acid and other carboxylic acids to generate methyl and alkyl radicals, respectively, without the need for stoichiometric base. This protocol is accepting of a broad scope of alkene and carboxylic acids, including challenging ones that produce highly reactive primary alkyl radicals and those containing functional groups that are susceptible to nucleophilic substitution such as alkyl halides. This methodology highlights the utility of using heterogeneous semiconductor photocatalysts such as TiO2 for promoting challenging organic syntheses that rely on highly reactive intermediates.
The synthesis of α-azidoesters and geminal triazides
Klahn, Philipp,Erhardt, Hellmuth,Kotthaus, Andreas,Kirsch, Stefan F.
supporting information, p. 7913 - 7917 (2014/08/05)
Three simple methods for the synthesis of geminal triazides are described: Starting from 1) 3-oxocarboxylic acids, 2) iodomethyl ketones, or 3) terminal olefins, a range of triazidomethyl ketones can be constructed under mild oxidative reaction conditions by the use of IBX-SO3K, a sulfonylated derivative of 2-iodoxybenzoic acid (IBX), and NaN3 as an azide source. This is the first report of representatives of this novel class of triazide compounds: Despite their high nitrogen content, the geminal triazides are easy to handle, even when preparative-scale syntheses are performed. (Caution: These procedures still require protective measures!) The triazides are now broadly available for further studies regarding their properties and reactivity. Furthermore, we show how the method can be used to provide α-azidoesters, which are potential building blocks for amino acids. Either/or: Geminal triazides are rapidly constructed with broad scope by the use of oxocarboxylic acids, iodomethyl ketones, or terminal olefins as starting substrates in oxidative azidations with a mild derivative of 2-iodoxybenzoic acid and sodium azide. Along with this little-studied class of organic azides, α-azidoesters were also synthesized.
METHOD FOR PRODUCING (4E)-5-CHLORO-2-ISOPROPYL-4-PENTENOATE AND OPTICALLY ACTIVE SUBSTANCE THEREOF
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Page/Page column 11; 12, (2010/11/27)
To provide a process for producing a (4E)-5-chloro-2-isopropyl-4-pentenoate in high yield and efficiently. A compound (2) is reacted with a base in the presence of an aprotic solvent and then with (1E)-1,3-dichloro-1-propene in the same reaction vessel to obtain a compound (3), and then either of -COOR moieties in the compound (3) is replaced with a hydrogen atom in the same reaction vessel to obtain a compound (4): wherein R is a lower alkyl group or an aralkyl group.
PROCESSES FOR PRODUCING (4E)-5-CHLORO-2-ISOPROPYL-4-PENTENOIC ESTER AND OPTICALLY ACTIVE ISOMER THEREOF
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Page/Page column 11, (2008/06/13)
The present invention provides processes for producing a (4E)-5-chloro-2-isopropyl-4-pentenoate and an optical isomer of the (4E)-5-chloro-2-isopropyl-4-pentenoate, namely a process for producing a (4E)-5-chloro-2-isopropyl-4-pentenoate represented by the following formula (4), which comprises reacting a compound represented by the following formula (2) in the presence of an aprotic solvent (II) with a base (II) and then with (1E)-1,3-dichloro-1-propene to give a compound represented by the following formula (3), and dealkoxycarbonylating either ester in the compound represented by the following formula (3), and a process for producing a (S)-(4E)-5-chloro-2-isopropyl-4-pentenoate represented by the following formula (5), which comprises optically resolving a (4E)-5-chloro-2-isopropyl-4-pentenoate represented by the formula (4) obtained by the above-mentioned process (wherein R is a lower alkyl group or an aralkyl group).
1,3-Stereoinduction in radical reactions: Radical additions to dialkyl 2-alkyl-4-methyleneglutarates
Hayen,Koch,Saak,Haase,Metzger
, p. 12458 - 12468 (2007/10/03)
Tin hydride-mediated radical additions to a series of α-methylene-glutarates 1, furnishing 2;4-dialkyl-substituted glutarates 3 are reported. The diastereoselectivity of hydrogen transfer to the intermediate adduct radicals 2, possessing a stereogenic center in γ-position, was disappointing in the temperature range of -78 to 80 °C. However, the reactions proved to be able to proceed with excellent 1,3-diastereoselectivities under chelation-controlled conditions, depending on the steric impacts of 2- and 4-alkyl substituents as well as on the ester-alkyl moiety and choice of Lewis acid. Using MgBr2·OEt2 as additive, syn-selectivities of 98:2 were achieved upon initial tert-butyl radical addition at -78 °C. High anti-diastereoselectivities were observed in the MgBr2·OEt2-controlled pathway at 70 °C when smaller alkyl radicals such as cyclohexyl, ethyl, and methyl were applied. Interesting and uncommon temperature dependences were observed in the temperature range of -78 to 100 °C, revealing strong entropic effects in the transition states. A model that accounts for the opposed stereochemical outcomes under chelation-controlled conditions is presented.
Electrochemically induced oxidative rearrangement of alkylidenemalonates
Elinson, Michail N.,Feducovich, Sergey K.,Nikishin, Gennady I.
, p. 14529 - 14540 (2007/10/03)
Alkylidenemalonates capable of double bond migration being electrolyzed in methanol or ethanol in the presence of alkali metal halides in an undivided cell equipped with Fe cathode are transformed into 2-alkyl-3,3- dimethoxyalkane-1,2-dicarboxylates in 70-90% yield via electrochemically induced oxidative rearrangement. Acidification of the reaction mixture after the electrolysis leads to the formation of 2-alkyl-3-oxoalkane-1,1- dicarboxylates. In the case of isobutylidenemalonate, the electrolysis intermediate dimethyl 3,3-dimethyl-2-methoxy-cyclopropane-1,1-dicarboxylate was isolated in 70% yield.
Electrochemical Cyclodimerization of Alkylidenemalonates
Elinson, Michail N.,Feducovich, Sergey K.,Zakharenkov, Alexandre A.,Ugrak, Bogdan I.,Nikishin, Gennady I.,et al.
, p. 5035 - 5046 (2007/10/02)
Electrolysis of dimethyl alkylidenemalonates RCH=C(COOMe)2 (R=n-Alk, Ph) in an undivided cell in MeOH in the presence of alkali metal halide as mediator, leads to the formation of cyclic dimers, i.e., 3,4-disubstituted 1,1,2,2-cyclobutanetetracarboxylates.The reaction proceeds via the reductive coupling of two substrate molecules at cathode and the cyclization of a hydrodimer dianion by its interaction with an active form of a mediator, an anode-generated halogen.
Enzymes in organic synthesis 51. Probing the dimensions of the large hydrophobic pocket of the active site of pig liver esterase
Provencher,Wynn,Jones,Krawczyk
, p. 2025 - 2026 (2007/10/02)
The dimensions of the large hydrophobic pocket (H(L)) of the active site model of pig liver esterase (PLE) were probed using a series of aliphatic and phenylic malonates. Results from the hydrolyses of these new unnatural substrates permitted the extension of the H(L) pocket to give the new dimensions of 6.2 x 2.3 x 3.9 A for a total volume of ~56 A3.
Synthetic approach to identification of periplaneta sex pheromones
Harada, Takeo,Takahashi, Takashi,Takahashi, Shozo
, p. 369 - 372 (2007/10/02)
Syntheses of the proposed structure of periplanone J (1) and its epimer 2, and the discussion on the true structure of PJ based on the spectral study of 1,2 and the natural PJ are described.
Hydrogenolysis of Small Cycloalkanes, XVII. - Catalytic Hydrogenation of Dimethyl Bicyclobutane-2,2-dicarboxylate
Frank, Juergen,Konrad, Gerd,Rossnagel, Ingrid,Musso, Hans,Maier, Guenther,Schwab, Wolfgang
, p. 443 - 444 (2007/10/02)
Catalytic hydrogenation of the title compound 1 yields 92-95percent of ethyl methyl malonate (2), 3-5percent of n-propyl malonate (3), 2-3percent of dimethyl 2-methyl-1,1-cyclopropanedicarboxylate (4), and no 1,1-cyclobutanedicarboxylate 5, the formation of which, however, can be induced with a poisoned catalyst.