7152-32-1Relevant articles and documents
Overcoming Kinetic and Thermodynamic Challenges of Classic Cope Rearrangements
Fereyduni, Ehsan,Lahtigui, Ouidad,Sanders, Jacob N.,Tomiczek, Breanna M.,Mannchen, Michael D.,Yu, Roland A.,Houk,Grenning, Alexander J.
, p. 2632 - 2643 (2021/02/05)
Systematic evaluation of 1,5-dienes bearing 3,3-electron-withdrawing groups and 4-methylation results in the discovery of a Cope rearrangement for Meldrum's acid-containing substrates that have unexpectedly favorable kinetic and thermodynamic profiles. The protocol is quite general due to a concise and convergent synthesis from abundant starting materials. Furthermore, products with an embedded Meldrum's acid moiety are prepared, which, in turn, can yield complex amides under neutral conditions. We have now expanded the scope of the reductive Cope rearrangement, which, via chemoselective reduction, can promote thermodynamically unfavorable [3,3] sigmatropic rearrangements of 3,3-dicyano-1,5-dienes to form reduced Cope rearrangement products. The Cope rearrangement is found to be stereospecific and can yield enantioenriched building blocks when chiral, nonracemic 1,3-disubstituted allylic electrophiles are utilized. We expand further the use of Cope rearrangements for the synthesis of highly valuable building blocks for complex- and drug-like molecular synthesis.
FRAGRANCE AND FLAVOR MATERIALS
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Page/Page column 33; 34; 46, (2019/12/28)
The synthesis and application of compounds having unique and desired flavor and/or fragrance characteristics are provided herein. The compounds herein can be employed alone or incorporated as fragrance or flavor ingredients in fragrance or flavor compositions. The application is also directed to consumer products comprising such derivatives and/or fragrance or flavor compositions.
Gram-scale preparation of dialkylideneacetones through Ca(OH)2-catalyzed Claisen-Schmidt condensation in dilute aqueous EtOH
Zhang, Hao,Han, Mengting,Yang, Chenggen,Yu, Lei,Xu, Qing
, (2018/02/06)
A synthetic method of dialkylideneacetones has been developed. Compared with known protocols, the method employed catalytic Ca(OH)2 as the cheap, mild base catalyst and dilute aqueous EtOH (20%, v/v) as the green and safe solvent. The procedure was easily operated: In most cases, the product could be isolated by a simple filtration, and purified by washing with water. This paper provided experimental details of the reactions, which could be applied in gram-scale synthesis and should be a very reliable and practical protocol to prepare these useful compounds in laboratory and at the industrial level.
Monodisperse amorphous CuB23 alloy short nanotubes: Novel efficient catalysts for Heck coupling of inactivated alkyl halides and alkenes
Yang, Fan,Fu, Shi Yan,Chu, Wei,Li, Chun,Tong, Dong Ge
, p. 45838 - 45843 (2015/02/19)
Heck-type coupling of inactivated alkyl halides and alkenes, catalyzed by amorphous CuB23 alloy short nanotubes, has been developed. Such couplings occur on the surfaces of nanotubes via a single-electron oxidative reaction. The results indicate that CuB23 nanotubes are efficient catalysts to replace Pd and Ni complexes for such Heck-type coupling. This journal is
Catalysis by metal-organic frameworks: Proline and gold functionalized MOFs for the aldol and three-component coupling reactions
Lili, Liu,Xin, Zhang,Shumin, Rang,Ying, Yang,Xiaoping, Dai,Jinsen, Gao,Chunming, Xu,Jing, He
, p. 13093 - 13107 (2014/04/03)
Translation of homogeneous catalysis into heterogeneous catalysis is a promising solution to green and sustainable development in the chemical industry. Recent research has shown that metal-organic frameworks (MOFs) could bridge the gap between homogeneous and heterogeneous catalysis. We successfully prepared for the first time a novel homochiral Zn-containing MOF referred to as CUP-1 based on the mixed linkers of 2-aminoterephthalic acid and l-lactic acid in a one-pot synthesis. The free NH2 group in the homochiral framework of CUP-1, similar to the well known achiral IRMOF-3, is potentially available for undergoing a variety of organic transformations, as demonstrated by choosing the auxiliary chiral l-proline and nano gold to functionalize MOFs with postsynthetic modification and one-pot synthesis strategies. IRMOF-3, CUP-1 and their functionalized samples were in-depth characterized by X-ray diffraction, N2 adsorption-desorption, optical and transmission electron microscopy, infrared spectroscopy, solid state nuclear magnetic resonance, thermogravimetric and differential thermal analysis, and temperature-programmed reduction. l-Proline functionalized IRMOF-3 shows fair to excellent enantioselectivity (up to 98%) in asymmetrical aldol reactions of aldehydes and acetone with higher turnover numbers and catalytic stabilities than the homogeneous counterpart. The gold functionalized CUP-1 catalysts are found to be highly active, stable and reusable for the three-component coupling reactions of aldehydes, alkynes and amines. This work provides general methods to functionalize MOFs with the active ligand and metal nanoparticles for fabrication of highly efficient MOF-based heterogeneous catalysts. This journal is the Partner Organisations 2014.
Reversal of enantioselectivity in aldol reaction: New data on proline/λ-alumina organic-inorganic hybrid catalysts
Sz?ll?si, Gyo?rgy,Fekete, Mónika,Gurka, András A.,Bartók, Mihály
, p. 478 - 486 (2014/06/24)
We report new results on the aldol reactions between aldehydes of three different types (aromatic, aliphatic and cycloaliphatic) and acetone/cycloalkanones as reaction partners, driven by organic-inorganic hybrid catalyst Pro/λ-Al2O3. In contrast to the homogeneous liquidphase reaction, over Pro/λ-Al2O 3reversal of the enantioselection in up to 20-40 % ee depending on the structure of the aldehyde was observed in reactions of acetone. Reversal of the ee in the presence of c-Al2O3cannot be generalized, as it has only been observed for acetone among the ketones studied by us. It was proven using methods of a great variety such as ultrasonic irradiation, reuse measurements on used catalyst and the filtrate of the first reaction, measurements on the L-Pro-L-Pro(OH) dipeptide, studies using mixtures of L-Pro and D-Pro that the organic-inorganic hybrid catalyst Pro/λ-Al 2O3formed in situ is responsible for reversal of the ee. In the reactions of cycloalkanones there is presumably competition between the liquid-phase and the surface reaction over Pro/ c-Al2O 3with preference for the former. Based on these results a surface reaction pathway was proposed. Although, the ees obtained under heterogeneous catalytic conditions are low, further studies may lead to application of this unusual phenomenon for obtaining chiral heterogeneous catalysts suitable for the preparation of the desired enantiomer of a chiral compound using the same chiral source. Springer Science+Business Media New York 2013.
Enantioselective [4 + 2] cycloaddition of cyclic N-sulfimines and acyclic enones or ynones: A concise route to sulfamidate-fused 2,6-disubstituted piperidin-4-ones
Liu, Yong,Kang, Tai-Ran,Liu, Quan-Zhong,Chen, Lian-Mei,Wang, Ya-Chuan,Liu, Jie,Xie, Yong-Mei,Yang, Jin-Liang,He, Long
, p. 6090 - 6093 (2014/01/06)
A concise route to valuable sulfamate-fused 2,6-disubstituted piperidin-4-ones or 2,3-dihydropyridin-4(1H)-ones in good yield with high diastereo- and enantioselectivity is presented. The combination of chiral primary amine and o-fluorobenzoic acid efficiently promoted an asymmetric [4 + 2] cycloaddition reaction of N-sulfonylimines and enones or ynones. The cycloaddition reaction between cyclic N-sulfonylimines and ynones is first reported.
COMPOUNDS AND METHODS FOR ALTERING LIFESPAN OF EUKARYOTIC ORGANISMS
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Page/Page column 17, (2011/06/19)
Provided are compounds which generally have a triketone structure. Examples of the compounds include derivatives of 1,3-cyclohexanedione, such as: 1,3-cyclohexanedione, 2-propanoyl-5-cyclohexyl-; 1,3-cyclohexanedione, 2-propanoyl-5-[4-fluorophenyl]-; 1,3-cyclohexanedione, 2-acetyl-5-[thien-2-yl]-; 1,3-cyclohexanedione, 2-acetyl-5 -butyl-; and 1,3-cyclohexanedione, 2-propanoyl-5-[bicyclo[2.2.1]hept-2-en-5-yl]-. The compounds can be used to alter the lifespan of eukaryotic organisms and treat inflammation.
Synthesis and anti-migrative evaluation of moverastin derivatives
Sawada, Masato,Kubo, Shin-Ichiro,Matsumura, Koji,Takemoto, Yasushi,Kobayashi, Hiroki,Tashiro, Etsu,Kitahara, Takeshi,Watanabe, Hidenori,Imoto, Masaya
scheme or table, p. 1385 - 1389 (2011/04/23)
Cell migration of tumor cells is essential for invasion of the extracellular matrix and for cell dissemination. Inhibition of the cell migration involved in the invasion process represents a potential therapeutic approach to the treatment of tumor metastasis; therefore, a novel series of derivatives of moverastins (moverastins A and B), an inhibitor of tumor cell migration, was designed and chemically synthesized. Among these moverastin derivatives, several compounds showed stronger cell migration inhibitory activity than parental moverastins, and UTKO1 was found to have the most potent inhibitory activity against the migration of human esophageal tumor EC17 cells in a chemotaxis cell chamber assay. Interestingly, although moverastins are considered to inhibit tumor cell migration by inhibiting farnesyltransferase (FTase), UTKO1 did not inhibit FTase, indicating that UTKO1 inhibited tumor cell migration by a mechanism other than the inhibition of FTase.
Processes for preparing beta-hydroxy-ketones and alpha,beta-unsaturated ketones
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Page 17, (2008/06/13)
Processes for producing β-hydroxy-ketones and α,β-unsaturated ketones are disclosed which comprise the crossed condensation of an aldehyde with a ketone in the presence of a hydroxide or alkoxide of alkali metal or an alkaline earth metal as catalyst. The products of the process, β-hydroxy-ketones and α,β-unsaturated ketones, are useful for the preparation of many commercially important products in the chemical process industries including solvents, drug intermediates, flavors and fragrances, other specialty chemical intermediates.
