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61.
The synthesis of some novel bakkenolides and their epi-spiro analogues was achieved by a new approach. Photolysis of allyl 1-(phenylseleno)-2-oxocyclopentanecarboxylates 7-9 afforded the corresponding spiro lactones 10-12 by radical cyclization via group transfer of the phenylseleno group. Selenoxide elimination of 11 and 12 produced the corresponding beta-methylene lactones 14 and 15. Diels-Alder cycloaddition of lactone11 with piperylene failed at ambient pressure, but proceeded in generally good yield in the presence of various Lewis acids at pressures of ca. 16 kbar, to give mixtures of beta-exo, alpha-endo, and beta-endo cycloadducts 19, 21, and 23, respectively. The preponderance of endo products 21 and 23, formed via highly hindered, but more compact, transition states was attributed to the high pressure and resulted in trans-dimethyl configurations of the products. The facial selectivity was dependent upon the Lewis acids, and the greatest alpha:beta ratio was observed with catalysts of the type TiCl(2)(OR)(2). Epimerization of the C-4 methyl group in 21 and 23 to furnish the corresponding cis-dimethyl analogues was achieved via exo-epoxidation, regioselective reduction, oxidation to the corresponding 3-keto derivatives, and base-catalyzed equilibration, thereby affording (+/-)-3,6-dioxobakkenolide-A (39) and its epi-spiro derivative 28, respectively. When the radical cyclization step was performed subsequent to the Diels-Alder cycloaddition by photolysis of perhydrindane 43, only the epi-spiro product 44 was obtained. 相似文献
62.
Narayan G. Bhat Patricia Wawroski Gonzalo Perez-Garcia Mayra Elizondo 《Tetrahedron letters》2005,46(31):5153-5155
A convenient, novel diastereoselective synthesis of 1-trimethylsilyl-(E)-1,3-alkenynes and a convenient synthesis of alkyl trimethylsilylethynyl ketones based on Z-1-bromo-1-alkenylboronate esters are developed. α-Bromo-(Z)-1-alkenylboronate esters readily available using literature procedures smoothly undergo a reaction with trimethylsilylethynyllithium (derived from the deprotonation of trimethylsilylethyne with n-butyllithium) in tetrahydrofuran to provide the corresponding ‘ate’ complexes. These ‘ate’ complexes undergo intramolecular nucleophilic substitution reactions to afford the corresponding (E)-1-alkenylboronate esters containing trimethylsilylethynyl moiety which upon protonolysis with acetic acid provide the corresponding 1-trimethylsilyl-(E)-1,3-alkenynes in good yields (70-82%) and in high stereochemical purities (>98%). These intermediates upon oxidation with hydrogen peroxide and sodium acetate afford the corresponding alkyl trimethylsilylethynyl ketones in good yields (66-78%). 相似文献
63.
Alexis Rojas-Gonzlez Claudia Yuritzi Figueroa-Hernndez Oscar Gonzlez-Rios Mirna Leonor Surez-Quiroz Rosa María Gonzlez-Amaro Zorba Josu Hernndez-Estrada Patricia Rayas-Duarte 《Molecules (Basel, Switzerland)》2022,27(11)
The demand of foods with high antioxidant capacity have increased and research on these foods continues to grow. This review is focused on chlorogenic acids (CGAs) from green coffee, which is the most abundant source. The main CGA in coffee is 5-O-caffeoylquinic acid (5-CQA). Coffee extracts are currently the most widely used source to enhance the antioxidant activity of foods. Due to the solubility of CGAs, their extraction is mainly performed with organic solvents. CGAs have been associated with health benefits, such as antioxidant, antiviral, antibacterial, anticancer, and anti-inflammatory activity, and others that reduce the risk of cardiovascular diseases, type 2 diabetes, and Alzheimer’s disease. However, the biological activities depend on the stability of CGAs, which are sensitive to pH, temperature, and light. The anti-inflammatory activity of 5-CQA is attributed to reducing the proinflammatory activity of cytokines. 5-CQA can negatively affect colon microbiota. An increase in anthocyanins and antioxidant activity was observed when CGAs extracts were added to different food matrices such as dairy products, coffee drinks, chocolate, and bakery products. The fortification of foods with coffee CGAs has the potential to improve the functionality of foods. 相似文献
64.
65.
Michèle Postel Félix Tomi Henri Li Kam Wah Laurence Mordenti Patricia Guillaume 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-4):453-457
Abstract Fe(NO)2XL and Fe(NO)X2L nitrosyl iron complexes, X = Cl, I, and L = HMPA, dppe, PPh3, activate molecular O2 to yield nitrato complexes. The phosphorous ligand is decisive for the oxidative power of these nitrates: with HMPA or dppe, oxygen transfer occurs only to phosphines. On going from HMPA to PPh3 the single nitrato complex obtained, Fe(NO)2X(OPPh3)2 selectively epoxidizes cyclohexene, and this is the first example of oxygen transfer from a nitrato ligand to an olefin. 相似文献
66.
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68.
Núbia Boechat Jorge Carlos Santos da Costa Jorge de Souza Mendonça Karla Ceodaro Paes Elisa Lopes Fernandes Pedro Santos Mello de Oliveira 《合成通讯》2013,43(24):3187-3190
Some heteroaromatic esters were reduced to the corresponding alcohols by using a sodium borohydride–methanol system. The reduction was completed within 0.15–2.0 h in refluxing THF. The alcohol products were isolated after aqueous workup in moderate to excellent yield (48–97%). 相似文献
69.
It has been shown that tert-butyldimethylsilylated (Z) 2-carboethoxymethylene cycloalkanols are readily desilylated with concomitant cyclization to give the corresponding butenolides. The (E) isomers are desilylated, but not cyclized under these conditions. 相似文献
70.
Robyn M. Lucas Patricia Valery Ingrid van der Mei Terence Dwyer Michael P. Pender Bruce Taylor Anne‐Louise Ponsonby The Ausimmune Investigator Group 《Photochemistry and photobiology》2013,89(3):737-744
Spatio‐temporal patterns in sun exposure underlie variations in skin cancer incidence and vitamin D deficiency, indicate effectiveness of sun protection programs and provide insights into future health risks. From 558 adults across four regions of Australia (Brisbane (27°S), Newcastle (33°S), Geelong and the Western Districts of Victoria (37°S) and Tasmania (43°S)), we collected: self‐report data on time‐in‐the‐sun from age 6 years; natural skin color and ethnicity; silicone skin casts (for cumulative skin damage); and serum for vitamin D status. Ambient ultraviolet radiation (UVR) at the location of residence, with time‐in‐the‐sun, was used to calculate a “UVR dose” for each year of life. Individuals maintained their ranking compared to their peers for time‐in‐the‐sun in summer compared to winter and across ages (Spearman rho 0.24–0.84, all P < 0.001). Time‐in‐the‐sun decreased with age in all birth cohorts, and over calendar time. Summer time‐in‐the‐sun increased with increasing latitude (P < 0.001). Seasonal variation in vitamin D status had greater amplitude and vitamin D deficiency increased with increasing latitude. Temporal patterns are consistent with effectiveness of sun protection programs. Higher relative time‐in‐the‐sun persists from childhood through adulthood. Lower summer time‐in‐the‐sun in the warmest location may have implications for predictions of UVR‐related health risks of climate change. 相似文献