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11.
A computational study on the intermolecular reaction of protonated oxirane with methylpropene, as a model for initiation of oxidosqualene cyclisation, shows that the SN2-like ring opening is strongly exothermic with a low barrier to reaction and establishes the geometry of the intermolecular reaction. 相似文献
12.
The biosynthesis of the potent environmental carcinogen aflatoxin B1 involves ca. 15 steps beyond the first polyketide intermediate. Central among these is the rearrangement of the anthraqinone versicolorin A to the xanthone demethylsterigmatocystin. Genetic evidence strongly suggests that two enzymes are required for this process, a cytochrome P450, AflN, and a probable NADPH-dependent oxidoreductase, AflM. Given the overall redox change evident in this skeletal rearrangement, two rounds of oxidation and a reduction necessarily occur. Earlier experiments indicated that reductive deoxygenation of versicolorin A is not the first step. In the present report we consider a mechanistic alternative that AflM-mediated reduction is instead the last of these three reactions prior to formation of the xanthone intermediate. To this end, 9-hydroxydihydrodemethylsterigmatocystin was prepared by total synthesis as was its 9-deoxy analogue, an established aflatoxin precursor. During the final isolation of the "angular" synthetic xanthone targets it was found that acid catalysis promoted their isomerization to thermodynamically favored "linear" xanthones. Whole-cell and ground-cell incubations of the 9-hydroxy- and 9-deoxyxanthones were conducted with a mutant strain of Aspergillus parasiticus blocked at the first step of the pathway and examined for their ability to support aflatoxin production. The 9-deoxyxanthone gave dramatically enhanced levels of the mycotoxin. The 9-hydroxyxanthone, on the other hand, afforded no detectable increase in aflatoxins above controls, indicating that reductive deoxygenation at C-9 of a xanthone precursor does not take place in aflatoxin biosynthesis. Constraints imposed by earlier studies and the experiments in this paper serve to eliminate simple and intuitive conversions of versicolorin A to demethylsterigmatocystin and lead inescapably to a more subtle reaction sequence of oxidation-reduction-oxidation. Previous puzzling observations of extensive A-ring hydrogen exchange in the course of the rearrangement of versicolorin A to demethylsterigmatocystin have now been explained by a new mechanism that is consistent with all extant data. We propose that P450-mediated aryl epoxidation (AflN) initially disrupts the aromatic A-ring of versicolorin A. Oxirane opening enables A-ring proton exchange, as does the subsequent AflM-mediated reductive step. A second cycle of P450 oxidation (AflN), this time a Baeyer-Villiger cleavage, enables decarboxylation and the formation of demethylsterigmatocystin. Mechanistic and stereoelectronic principles that underlie this proposal are described and may prove general as illustrated in biogenetic hypotheses for four other fungal anthraquinone --> xanthone transformations. 相似文献
13.
14.
Zhou J Kelly WL Bachmann BO Gunsior M Townsend CA Solomon EI 《Journal of the American Chemical Society》2001,123(30):7388-7398
Using a single ferrous active site, clavaminate synthase 2 (CS2) activates O(2) and catalyzes the hydroxylation of deoxyguanidinoproclavaminic acid (DGPC), the oxidative ring closure of proclavaminic acid (PC), and the desaturation of dihydroclavaminic acid (and a substrate analogue, deoxyproclavaminic acid (DPC)), each coupled to the oxidative decarboxylation of cosubstrate, alpha-ketoglutarate (alpha-KG). CS2 can also catalyze an uncoupled decarboxylation of alpha-KG both in the absence and in the presence of substrate, which results in enzyme deactivation. Resting CS2/Fe(II) has a six-coordinate Fe(II) site, and alpha-KG binds to the iron in a bidentate mode. The active site becomes five-coordinate only when both substrate and alpha-KG are bound, the latter still in a bidentate mode. Absorption, CD, MCD, and VTVH MCD studies of the interaction of CS2 with DGPC, PC, and DPC provide significant molecular level insight into the structure/function correlations of this multifunctional enzyme. There are varying amounts of six-coordinate ferrous species in the substrate complexes, which correlate to the uncoupled reaction. Five-coordinate ferrous species with similar geometric and electronic structures are present for all three substrate/alpha-KG complexes. Coordinative unsaturation of the Fe(II) in the presence of both cosubstrate and substrate appears to be critical for the coupling of the oxidative decarboxylation of alpha-KG to the different substrate oxidation reactions. In addition to the substrate orientation relative to the open coordination position on the iron site, it is hypothesized that the enzyme can affect the nature of the reactivity by further regulating the binding energy of the water to the ferrous species in the enzyme/succinate/product complex. 相似文献
15.
Condensation of 3,4-dichloro-6-[(trimethylsilyl)oxy] pyridazine ( 3 ) with 1-O-acetyl-2,3,5-tri-O-benzoyl-β- D -ribofuranose ( 4 ), by the stannic chloride catalyzed procedure, has furnished 3,4-dichloro-1-(2,3,5-tri-O-benzoyl-β- D -ribofuranosyl) pyridazin-6-one ( 5 ). Nucleophilic displacement of the chloro groups and removal of the benzoyl blocking groups from 5 has furnished 3-chloro-4-methoxy-, 3,4-dimethoxy-, 4-amino-3-chloro-, 3-chloro-4-methylamino-, 3-chloro-4-hydroxy-, and 4-hydroxy-3-methoxy-1-β- D -ribofuranosylpyridazin-6-one. An unusual reaction of 5 with dimethylamine is reported. Condensation of 4,5-dichloro-3-nitro-6-[(trimethylsilyl)oxy]pyridazine with 4 yielded 4,5-dichloro-3-nitro-1-(2,3,5-tri-O-benzoyl-β- D -ribofuranosyl)pyridazin-6-one ( 24 ). Nucleophilic displacement of the aromatic nitro groups from 24 is discussed. Condensation of 3 with 3,5-di-O-p-toluoyl 2-deoxy- D -erythro-pentofuranosyl chloride ( 28 ) afforded an α, β mixture of 2-deoxy nucleosides. The synthesis of certain 3-substituted pyridazine 2′-deoxy necleosides are reported. 相似文献
16.
P. F. Crain James A. McCloskey Arthur F. Lewis Karl H. Schram Leroy B. Townsend 《Journal of heterocyclic chemistry》1973,10(5):843-847
The mass spectrum of pyrazomycin has been obtained and reveals a fragmentation pattern with several important peaks which are not normally found in the mass spectra of C-nucleosides. It has now been established, using model compounds, that these unusual fragment ions are a direct result of the juxtaposition of the exocyclic hydroxy and carboxamido groups of the aglycon. It appears that a facile elimination of ammonia and ethanol from o-hydroxycarboxamides and o-hydroxyethylesters, respectively, may be a general fragmentation reaction for aromatic heterocycles. A mass spectrum of the TMS derivative of pyrazomycin has also been obtained and factors which may result in exceptions to the empirical B+30 (M-103) rule for C-nucleosides are discussed. 相似文献
17.
The synthesis of 3-cyano-2-(β-D-ribofuranosyl)indazole (4) has been accomplished by a condensation of N-trimethylsilyl-3-cyanoindazole (1) with 2,3,5-tri-O-aeetyl-D-ribofuranosyl bromide (2) followed by subsequent deacetylation. The reactivity of the 3-cyano group was demonstrated by the conversion of 4 to 2-(β-D-ribofuranosyl)indazole-3-carboxamide (5) and 2-(β-D-ribofuranosyl)indazole-3-thiocarboxamide (6). The site of ribosylation and the assignment of anomeric configuration for 4 is discussed. The magnetic anisotropy effect of the exocyclic group at C3 on the anomeric proton as determined by pmr spectroscopy is discussed. 相似文献
18.
Richard L. Tolman Roland K. Robins Leroy B. Townsend 《Journal of heterocyclic chemistry》1971,8(5):703-706
A study involving the reactivity of the pyrrolo[2,3-d] pyrimidine ring system at position 6 with another exocyclic group (CN or -NH2) already residing at C5 has established that hydrogen and bromine are susceptible to electrophilic and acid-catalyzed nucleophilic substitution, respect-tively. In one instance a strong nucleophile (hydrazine) gave nucleophilic substitution at position 6 which was followed by a reaction with the o-nitrile group to afford the tricyclic nucleoside 4,5-diamino-8-(β-D-ribofuranosyl)pyrazolo[3′, 4′ :5,4] pyrrolo[2,3-d] pyrimidine (4). 相似文献
19.
Infrared and Raman spectra have been obtained for benzyl fluoride and a vibrational assignment has been made. The spectra indicate the presence of a large number of conformers that differ only in the orientation of the C-F bond, as a result of free or nearly free internal rotation. 相似文献
20.
The synthesis of 5,6-dichloro-1-(β-D -ribofuranosyl)benzotriazole ( 4a ), 5,6-dimethyl-1-(β-D -ribofuranosyl)benzotriazole ( 4b ) and 1-(β-D -ribofuranosyl)benzotriazole ( 4c ) in good yield has been accomplished by the condensation of the appropriate 1-trimethylsilylbenzotriazole ( 1a, 1b , and 1c ) with 2,3,5-tri-O-acetyl-D -ribofuranosyl bromide (2) followed by subsequent deacetylation of the reaction products. The assignment of anomeric configuration and site of glycosidation for all nucleosides reported is discussed. 相似文献