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101.
Diaryliodonium salts are demonstrated as efficient arylating agents of aliphatic alcohols under metal-free conditions. The reaction proceeds at room temperature within 90 min to give alkyl aryl ethers in good to excellent yields. Aryl groups with electron-withdrawing substituents are transferred most efficiently, and unsymmetric iodonium salts give chemoselective arylations. The methodology has been applied to the formal synthesis of butoxycaine. 相似文献
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— Propionibacterium acnes (P. acnes ), grown on Eagles medium with different pH. were irradiated with monochromatic light in the range 320 to 440 nm. Different pH leads to different porphyrin concentrations in the cells. The light sensitivity of the bacteria was estimated from the reduction in their ability to form colonies after radiation. The sensitivity was highest for the lowest wavelength (320 nm). and decreased continuously with increasing wavelength up to 380 nm. In the region between 380 and 440 nm there was a second maximum (at 415 nm) which corresponds to the maximum absorption ol the fluorescing porphyrins in P. acnes . The sensitivity to 415 nm light was found to be dependent on the endogenous porphyrin concentration in the cells. while the sensitivity to 320 nm radiation was independent of the amount of porphyrin present. These results indicate that porphyrins produced by the bacteria are important for the light sensitivity of these bacteria. 相似文献
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Pham AT Malterud KE Paulsen BS Diallo D Wangensteen H 《Natural product communications》2011,6(8):1125-1128
From a methanol extract of the leaves of the Malian medicinal tree Terminalia macroptera, cis-polyisoprene (1), chebulic acid trimethyl ester (2), methyl gallate (3), shikimic acid (4), corilagin (5), rutin (6), narcissin (7), chebulagic acid (8) and chebulinic acid (9), were isolated. Cispolyisoprene (1) was the major non-polar constituent. The novel compound 2 showed high radical scavenging activity (IC50 4.7 microg/mL), but was inactive as xanthine oxidase inhibitor. The major substituent of the crude extract, substance 5, showed a high radical scavenger effect (IC50 2.7 microg/mL) and weak xanthine oxidase inhibition (IC50 ca 105 microg/mL). The antioxidant and radical scavenging effects of some of the substances identified in this study may to some extent explain the medical use of this tree in West Africa. 相似文献
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Total Synthesis,Stereochemical Revision,and Biological Reassessment of Mandelalide A: Chemical Mimicry of Intrafamily Relationships 下载免费PDF全文
Dr. Jens Willwacher Dipl.‐Ing. Berit Heggen Conny Wirtz Prof. Walter Thiel Prof. Alois Fürstner 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(29):10416-10430
Mandelalide A and three congeners had recently been isolated as the supposedly highly cytotoxic principles of an ascidian collected off the South African coastline. Since these compounds are hardly available from the natural source, a concise synthesis route was developed, targeting structure 1 as the purported representation of mandelalide A. The sequence involves an iridium‐catalyzed two‐directional Krische allylation and a cobalt‐catalyzed carbonylative epoxide opening as entry points for the preparation of the major building blocks. The final stages feature the first implementation of terminal acetylene metathesis into natural product total synthesis, which is remarkable in that this class of substrates had been beyond the reach of alkyne metathesis for decades. Synthetic 1 , however, proved not to be identical with the natural product. In an attempt to clarify this issue, NMR spectra were simulated for 20 conceivable diastereomers by using DFT followed by DP4 analysis; however, this did not provide a reliable assignment either. The puzzle was ultimately solved by the preparation of three diastereomers, of which compound 6 proved identical with mandelalide A in all analytical and spectroscopic regards. As the entire “northern sector” about the tetrahydrofuran ring in 6 shows the opposite configuration of what had originally been assigned, it is highly likely that the stereostructures of the sister compounds mandelalides B–D must be corrected analogously; we propose that these natural products are accurately represented by structures 68 – 70 . In an attempt to prove this reassignment, an entry into mandelalides C and D was sought by subjecting an advanced intermediate of the synthesis of 6 to a largely unprecedented intramolecular Morita–Baylis–Hillman reaction, which furnished the γ‐lactone derivative 74 as a mixture of diastereomers. Whereas (24R)‐ 74 was amenable to a hydroxyl‐directed dihydroxylation by using OsO4/TMEDA as the reagent, the sister compound (24S)‐ 74 did not follow a directed path but simply obeyed Kishi’s rule; only this unexpected escape precluded the preparation of mandelalides C and D by this route. A combined spectroscopic and computational (DFT) study showed that the reasons for this strikingly different behavior of the two diastereomers of 74 are rooted in their conformational peculiarities. This aspect apart, our results show that the OsO4/TMEDA complex reacts preferentially with electron deficient double bonds even if other alkenes are present that are more electron rich and less encumbered. Finally, in a brief biological survey authentic mandelalide A ( 6 ) was found to exhibit appreciable cytotoxicity only against one out of three tested human cancer cell lines and all synthetic congeners were hardly active. No significant fungicidal properties were observed. 相似文献
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