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351.
Cyclization of tri- and tetrasubstituted dienones 1 under Lewis acidic conditions in the presence of triethylsilane led to formation of either silyl enol ethers 6 or cyclopentanones 7 in good to excellent yields, depending on work-up conditions. The proposed mechanism involves initial Nazarov cyclization to give oxyallyl intermediates 5, which are intercepted via intermolecular transfer of hydride. The reactions proceeded cleanly with as little as 2 equiv. of silane and in most cases catalytic amounts of Lewis acid could be used. Trapping with Et3SiD occurs at the less substituted terminus in unsymmetrical cases. 相似文献
352.
A total synthesis of bulgaramine has been accomplished with a longest linear sequence of eight steps and an overall yield of 23% from commercially available 3,4-dimethoxyphenethyl alcohol. An intramolecular cyclopentannulation reaction of a Fischer aminocarbene complex provided the key step and occurred under significantly milder conditions and in higher yields than those of other reported examples of this reaction type. The reaction solvent was a critical factor in the cyclopentannulation reaction, with measurable amounts of the desired product observed only when THF was utilized. The product yield could be further enhanced by the addition of two-electron donor ligands, demonstrating the first example of this effect on the thermal reaction of aminocarbene complexes with alkynes. 相似文献
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Radical addition to 2-cyclohexyl-5-methylidene-6-methyl-1,3-dioxan-4-one ( 2 ) affords stereoselectively 5,6-trans-products trans- 3 . The size of the radical has no influence on the selectivity. These trans-acetals are converted into threo-3-hydroxy-butanoates 4 . Methyl 2-methylidene-3-[(tert-butyl)diphenylsilyloxy]butanoate ( 5 ), treated under the same conditions, leads mainly to the erythro-isomer of 4 after deprotection. An influence of the steric bulkyness of the radical is observed. The stereochemical course of the reactions is discussed. 相似文献
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Towards a goal of detecting scaled-up DNA adducts as altered deoxynucleotides by mass spectrometry, we have set up a practical and general method for isolating DNA-derived deoxyribonucleoside-5'-monophosphates devoid of ribonucleotides starting with a 1 g sample of mammalian tissue. The method is practical because costs have been minimized, and it is general because it can be applied to a more difficult sample such as mouse skin or non-fresh calf liver. The procedure, consisting of a series of steps that were largely gleaned and tuned from prior literature, proceeds as follows: (1) homogenize the tissue in sodium dodecyl sulfate; (2) digest with ribonuclease A, ribonuclease TI, alpha-amylase and proteinase K; (3) partition between water and phenol; (4) precipitate the DNA with ethanol followed by redissolving and dialysis; and (5) digest with nuclease P1 and phosphodiesterase I followed by ultrafiltration and boric acid gel chromatography. The yellow to brown color of DNA from difficult tissues only persisted up to the ultrafiltration step. Apparently this DNA was contaminated with iron-containing proteins. Residual ribonucleotides were not observable (<0.1%) by HPLC in the final sample. Without boric acid gel chromatography, residual contamination by ribonucleotides was about 1% even when the DNA was purified before digestion by phenol partitioning followed by use of a Genomic Tip kit from Qiagen. 相似文献
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