Search results for "Radical cyclization"
showing 8 items of 8 documents
Synthesis of (-)-Cryptopleurine by Combining Gold(I) Catalysis with a Free Radical Cyclization (Eur. J. Org. Chem. 10/2015)
2015
Radical Cyclization and 1,5-Hydrogen Transfer in Selected Aromatic Diazonium Salts
2014
2-(Methyl(3-methyl-1-phenyl-1H-pyrazol-5-yl)carbamoyl)thiophene-3-diazonium hydrogen sulfate 20, 2-(methyl(3-methyl-isoxazol-5yl)carbamoyl)-benzenediazonium hydrogen sulfate 21 and 2-(methyl(phenyl)carbamoyl)-benzenediazonium hydrogen sulphate 22 were synthesized and reacted with a CuSO4/NaCl/ascorbic acid combination to give complex mixtures. The structures of the reaction products were elucidated, depending upon the pathways followed. Compound 20 almost exclusively afforded an Ar-5 cyclization product and trace amounts of the product derived from a competing Ar-6 Pschorr closure. In the case of compound 21, the Ar-6 cyclization was not observed, while the Ar-5 cyclization and 1,5-hydrogen…
Synthesis of (-)-Cryptopleurine by Combining Gold(I) Catalysis with a Free Radical Cyclization
2015
(R)-(–)-Cryptopleurine, a highly cytotoxic alkaloid found in Cryptocarya and Boehmeria species, was synthesized in high optical purity using a gold(I)-NHC catalyzed cyclization of an unsymmetrical phenanthrene precursor combined with a free radical cyclization to achieve closure of the C-ring.
CuCl catalyzed radical cyclisation of N-alpha-perchloroacyl-ketene-N,S-acetals: a new way to prepare disubstituted maleic anhydrides
2012
The discovery that cycloalkanes can form thermomorphic systems with typical polar organic solvents has led to the development of less-polar electrolyte solutions. Their mixing and separation can be regulated reversibly at a moderate temperature range. The phase switching temperature can be controlled by changing the solvent compositions. While biphasic conditions are maintained below the phase switching temperature, conductive monophasic conditions as less-polar electrolyte solutions are obtained above the phase switching temperature. After the electrochemical transformations, biphasic conditions are reconstructed below the phase switching temperature, facilitating the separation of cycloal…
A green way to gamma-lactams through a copper catalyzed ARGET-ATRC in ethanol and in the presence of ascorbic acid
2011
Abstract A ‘green’ ARGET-ATRC, for the CuCl[PMDETA] catalysed cyclo -isomerization of N -allyl-α-polychloroamides to γ-lactams is described. The process works efficiently (yields 78–96%), uses a bio-solvent, as ethanol, and exploits the reducing feature of ascorbic acid to limit, at a low level (2–4%), the amount of catalyst. To preserve the efficacy of the catalytic cycle, addition of Na 2 CO 3 is essential, which quenches the HCl released during the CuCl[PMDETA] regeneration step. Profitable features of the process are: mild reaction temperatures (25–37 °C), relatively short reaction times (usually 5 h) and low solvent volumes (2 mmol of substrate/mL of ethanol). The method, upon stoichio…
The Reaction Mechanism of Spirocylization and Stereoselectivity Studies for the Calyculin C16 -C25 Fragment
2005
The mechanism of the double intramolecular hetero-Michael addition, a key reaction in the planned synthesis of the natural product calyculin C, has been studied by NMR. The cyclization follows Baldwin’s rules and proceeds first through a six-membered ring closure (6-endo-dig), followed by a five-membered ring cyclization (5-exo-trig). (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Total synthesis and biological evaluation of the natural product (−)-cyclonerodiol, a new inhibitor of IL-4 signaling
2014
In a screening program of natural compounds from fungi, the known cyclopentanoid sesquiterpene (-)-cyclonerodiol was identified as a specific inhibitor of the IL-4 induced STAT6 signaling pathway (IC50 = 9.7 μM) which is required for the differentiation of naive CD4 T cells to T helper type 2 (Th2) lymphocytes. As many allergic conditions, including allergic asthma and atopic diseases, are driven by an excessive Th2 response, STAT6 is a promising target for the development of new therapeutics. The compound was synthesized in six steps from (-)-linalool using an epoxide radical cyclization as the key step.
Total Synthesis of Phenanthroindolizidine Alkaloids by Combining Iodoaminocyclization with Free Radical Cyclization
2016
A concise and modular synthesis of phenanthroindolizidine alkaloids was achieved by combining iodoaminocylization with a free radical cyclization approach. The route described allowed the preparation of (±)-tylophorine, (±)-antofine, and (±)-deoxypergularinine in six steps. When commercially available l-prolinol was used as a chiral building block, (S)-(+)-tylophorine was also synthesized in 49% yield and >99% ee over five linear steps.