80904-75-2Relevant academic research and scientific papers
Photochemical reactions of prop-2-enyl and prop-2-ynyl substituted 4-aminomethyl- and 4-oxymethyl-2(5H)-furanones
Fort, Diego A.,Woltering, Thomas J.,Alker, Andre M.,Bach, Thorsten
, p. 1079 - 1100 (2014/01/17)
Compounds with a heterocyclic 9-oxatricyclo[5.3.0.01,5]decan-8-one skeleton were synthesized by intramolecular [2+2] photocycloaddition reactions of the title compounds (λ= 254 nm, Et2O or MeCN as the solvent). Starting from various substituted 4-(prop-2-enylaminomethyl)-2(5H)-furanones, products 5, 9, 18, 21, 23, 24 were obtained, which bear a nitrogen atom in position 3 of this skeleton within a pyrrolidine ring. The Boc or Cbz groups represent suitable nitrogen protecting groups, which were compatible with the irradiation conditions and which can be easily cleaved. In an analogous fashion an oxygen (product 22) and carbon substituent (product 25) could be implemented at position 3 of the product if the starting material was appropriately chosen. The prop-2-ynyl substituted substrates did not produce a [2+2] photocycloaddition product but rather underwent a cyclization to spiro products 11 and 13.
Application of the palladium-catalysed norbornene-assisted catellani reaction towards the total synthesis of (+)-linoxepin and isolinoxepin
Qureshi, Zafar,Weinstabl, Harald,Suhartono, Marcel,Liu, Hongqiang,Thesmar, Pierre,Lautens, Mark
supporting information, p. 4053 - 4069 (2014/07/08)
Our ongoing effort towards the development of highly selective transition-metal-catalysed C-H activation processes has led to the expansion of the Catellani reaction. In a Pd0/PdII/Pd IV-catalysed domino reaction, an aryl iodide, alkyl iodide and tert-butyl acrylate were combined to synthesize the carbon framework of the novel lignan (+)-linoxepin. The enantioselective synthesis highlights the work accomplished in our group and provides an excellent procedure for the reliable and scalable synthesis of architecturally complex scaffolds. This report outlines the synthetic approaches towards this interesting class of biologically active molecules. After the key Catellani/Heck reaction, our synthesis features a Leimeux-Johnson oxidation and a titanium tetrachloride mediated aldol condensation. Finally, a tuneable Mizoroki-Heck reaction was performed to furnish not only the natural product (+)-linoxepin but also its isoform, which we have named isolinoxepin. The enantioselective total synthesis of the natural product (+)-linoxepin has been accomplished in eight steps starting from commercial materials. The key Pd-catalysed Catellani step served to combine aryl iodide, alkyl iodide and tert-butyl acrylate in a domino sequence. By tuning the final Heck reaction, both the natural product and its structural isomer were synthesized. Copyright
TRICYCLIC COMPOUNDS
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Paragraph 1317; 1318, (2014/06/25)
The present invention provides a compound of formula I or a pharmaceutically acceptable salt thereof; and its therapeutic uses. The present invention further provides a combination of pharmacologically active agents and a pharmaceutical composition.
Total synthesis of (+)-linoxepin by utilizing the catellani reaction
Weinstabl, Harald,Suhartono, Marcel,Qureshi, Zafar,Lautens, Mark
supporting information, p. 5305 - 5308 (2013/06/26)
Molecular intelligence: The structurally novel lignan (+)-linoxepin is synthesized in an eight-step sequence. The enantioselective synthesis features the palladium-catalyzed Catellani reaction as the key step. In this highly convergent multicomponent reaction, two new carbon-carbon bonds are formed, one of which results from a C-H bond functionalization. Copyright
Conformationally restricted pyrrolidines by intramolecular [2+2] photocycloaddition reactions
Fort, Diego A.,Woltering, Thomas J.,Nettekoven, Matthias,Knust, Henner,Bach, Thorsten
supporting information, p. 2989 - 2991 (2013/05/09)
Intramolecular [2+2] photocycloaddition reactions of diversely substituted N-Boc protected 4-(allylaminomethyl)-2(5H)-furanones resulted in rigid products (53-75%) with three spatially defined positions for further functionalisation. The Royal Society of Chemistry.
Development of a scalable synthesis of (S)-3-fluoromethyl-γ- butyrolactone, building block for Carmegliptin's Lactam moiety
Adam, Jean-Michel,Foricher, Joseph,Hanlon, Steven,Lohri, Bruno,Moine, Gerard,Schmid, Rudolf,Wirz, Beat,Zutter, Ulrich,Stahr, Helmut,Weber, Martin
experimental part, p. 515 - 526 (2011/12/05)
Several new routes are reported for the synthesis of (S)-3-fluoromethyl- γ-butyrolactone. An asymmetric hydrogenation-based synthesis was chosen as the enabling route to produce the lactone on a 10-kg scale. A superior stereoselective route starting from (S)-tert-butyl glycidyl ether which afforded the desired lactone in three steps with ～50% overall yield was finally selected for further development and production.
Gas-phase fragmentation of γ-lactone derivatives by electrospray ionization tandem mass spectrometry
Crotti, Antonio E. M.,Bronze-Uhle, Erika S.,Nascimento, Paulo G. B. D.,Donate, Paulo M.,Galembeck, Sergio E.,Vessecchi, Ricardo,Lopes, Norberto P.
experimental part, p. 1733 - 1741 (2010/08/04)
Fragmentation reactions of β-hydroxymethyl-, β-acetoxymethyl- and β-benzyloxymethyl-butenolides and the corresponding γ-butyrolactones were investigated by electrospray ionization tandem mass spectrometry (ESI-MS/MS) using collision-induced dissociation (CID). This study revealed that loss of H2O [M+H-18]+ is the main fragmentation process for β-hydroxymethylbutenolide (1) and β-hydroxymethyl-γ- butyrolactone (2). Loss of ketene ([M+H-42]+) is the major fragmentation process for protonated β-acetoxymethyl-γ-butyrolactone (4), but not for β-acetoxymethylbutenolide (3). The benzyl cation (m/z 91) is the major ion in the ESI-MS/MS spectra of β-benzyloxymethylbutenolide (5) and β-benzyloxymethyl-γ-butyrolactone (6). The different side chain at the β-position and the double bond presence afforded some product ions that can be important for the structural identification of each compound. The energetic aspects involved in the protonation and gas-phase fragmentation processes were interpreted on the basis of thermochemical data obtained by computational quantum chemistry. Copyright
Process for the preparation of (S)-4-fluoromethyl-dihydro-furan-2-one useful in the preparation of the DPP-IV inhibitor (S)-1 ((2S,3S,11bS)-2-amino-9,10-dimethoxy-1,3,4,6,7, 11b-hexahydro-2h-pyrido[2,1-a] isoquinolin-3-yl)-4-fluoromethyl-pyrrolidin-2-one
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Page/Page column 12, (2008/06/13)
This invention relates to a process of the preparation of the novel intermediate (S)-4-fluoromethyl-dihydro-furan-2-one of the formula and with its use for the manufacture of pyrido[2,1-a]isoquinoline derivatives of the formula which are useful for the treatment and/or prophylaxis of diseases which are associated with DPP IV.
Synthesis and antiviral activity of apio dideoxy nucleosides with azido or amino substituent
Jeong, Lak Shin,Lee, Young A.,Moon, Hyung Ryong,Chun, Moon Woo
, p. 1473 - 1487 (2007/10/03)
Novel apio dideoxynucleosides with azido or amino substituent were synthesized starting from 1,3-dihydroxyacetone utilizing an acid-catalyzed 1,4conjugated addition as a key step and evaluated for antiviral activity. Unfortunately, they were found to be neither active against HIV-1, HSV-1,2 and poliovirus nor toxic.
Methylation-ring opening of 3,3-disubstituted 2,3-epoxy alcohols. Synthesis of chiral quaternary fragments for assembly of briaran diterpenes
Balasubramaniam, Rajiv P.,Moss, David K.,Wyatt, Justin K.,Spence, John D.,Gee, Arvin,Nantz, Michael H.
, p. 7429 - 7444 (2007/10/03)
Two chiral quaternary carbon-containing fragments suitable for elaboration to the briaran diterpenes were obtained by regioselective methylation of functionalized 3,3-disubstituted 2,3-epoxy-1-ols. The factors which favor methylation at the more hindered position of a trisubstituted 2,3-epoxy alcohol were determined.
