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1.
The preparation of 7-amino-2-(2′-pyridyl)quinoline-5,8-quinone-6′-carboxylic acid (4) constituting a potential minimum, potent pharmacophore of streptonigrin (1) and lavendamycin (2) , two structurally-related naturally-occurring antitumor-antibiotic, is detailed. In contrast to observations associated with streptonigrin and lavendamycin in which the C-6′ acid potentiates the antitumor, antimicrobial, and cytotoxic activity of the naturally-occurring, substituted 7-aminoquinoline-5,8-quinone AB ring systems, the C-6′ carboxylic acid of 4 diminishes the observed antimicrobial and cytotoxic properties of 7-amino-2-(2′-pyridyl)quinoline-5,8-quinone. 相似文献
2.
A short, asymmetric synthesis of the 1,2,9,9a-tetrahydrocyclopropa[c]benzo[e]indol-4-one (CBI) analogue of the CC-1065 and duocarmycin alkylation subunits is detailed that employs an effective enzymatic desymmetrization reaction of prochiral diol 12 using a commercially available Pseudomonas sp. lipase. The optically active monoacetate (S)-13 is furnished in exceptional conversions (88%) and optical purity (99% ee) and serves as an intermediate for the preparation of either enantiomer of CBI. Similarly, the Pseudomonas sp. lipase resolved the racemic intermediate 19, affording advanced intermediates of CBI in good conversions and optical purity (99% ee), and provided an alternative approach to the preparation of optically active CBI derivatives. 相似文献
3.
Density functional theory has been applied at the B3LYP/6-311+G(d,p)//B3LYP/6-31G(d) level to examine the energetics of alpha,beta- versus beta,gamma-unsaturation for some common organic functional groups. Specifically, the relative stabilities of allyl-X (H2C=CHCH2X) and 1-propenyl-X (H3CCH=CHX) isomers have been computed for X = methyl, vinyl, phenyl, formyl, acetyl, methoxy, methylthio, methylsulfinyl, methylsulfonyl, sulfamoyl, and methoxysulfonyl, and the results are compared to available experimental data. The intrinsic preference of 3 kcal/mol for the 1-propenyl isomer when X = CH3 is exceeded by 2-4 kcal/mol for first-row conjugating groups, but it is not met for the sulfur-containing groups. In particular, alpha,beta-unsaturation is favored by less than 1 kcal/mol for the sulfone and sulfonamide analogues, while it is preferred by 8 kcal/mol for the vinyl-substituted case. Detailed structural results and torsional energy profiles are also reported. 相似文献
4.
Wilkie GD Elliott GI Blagg BS Wolkenberg SE Soenen DR Miller MM Pollack S Boger DL 《Journal of the American Chemical Society》2002,124(38):11292-11294
The scope of intramolecular Diels-Alder and a novel tandem Diels-Alder/1,3-dipolar cycloaddition cascade of 1,3,4-oxadiazoles is disclosed. In the cases examined, the tandem cycloadditions construct three new rings with formation of four new C-C bonds and set all six stereocenters about a central six-membered ring in a single step including three contiguous and four total quaternary centers without a trace of a second diastereomer. 相似文献
5.
6.
Dale L. Boger 《Journal of heterocyclic chemistry》1996,33(5):1519-1531
A review of our studies of the inverse electron demand Diels-Alder reactions of heteroaromatic and acyclic azadienes is presented and the application of a N-sulfonyl-1-aza-1,3-butadiene [4+2] cycloaddition reaction in the total synthesis of natural and ent-fredericamycin A is described in detail. 相似文献
7.
A regiospecific total synthesis of juncusol () based on the use of two consecutive phenol annulations is detailed. 相似文献
8.
Buck SB Hardouin C Ichikawa S Soenen DR Gauss CM Hwang I Swingle MR Bonness KM Honkanen RE Boger DL 《Journal of the American Chemical Society》2003,125(51):15694-15695
Key derivatives and analogues of fostriecin were prepared and examined that revealed a fundamental role for the unsaturated lactone and confirmed the essential nature of the phosphate monoester. Thus, an identical 200-fold reduction in protein phosphatase 2A (PP2A) inhibition is observed with either the saturated lactone (7) or with an analogue that lacks the entire lactone (15). This 200-fold increase in PP2A inhibition attributable to the unsaturated lactone potentially may be due to reversible C269 alkylation within the PP beta12-beta13 active site loop accounting for PP2A/4 potency and selectivity. 相似文献
9.
A simple preparation of 2-carbomethoxy-2-azabicyclo[3.3.1]nonan-6-one ( and its conversion to the racemic benzomorphans: , , are described. 相似文献
10.
Two efficient methods are described for the selective modification of all six primary hydroxyl groups of α-cyclodextrin (α-CD, 1 1 ). One, using an indirect strategy, involves protection of all 18 hydroxyl functions as benzoate esters, followed by selective deprotection of the six primary alcohol groups. The other, using a direct strategy, involves selective activation of the primary hydroxyl groups via a bulky triphenylphosphonium salt, which is then substituted by azide anion as the reaction proceeds. A number of modified α-cyclodextrin derivatives have been prepared and fully characterized, among which are: the useful intermediate α-cyclodextrin-dodeca (2, 3) benzoate ( 3 ); hexakis (6-amino-6-deoxy)-α-cyclodextrin hexahydrochloride ( 7 ); hexakis (6-amino-6-deoxy)-dodeca (2, 3)-O-methyl-α-cyclodextrin hexahydrochloride ( 9 ), hexa (6)-O-methyl-α-cyclodextrin ( 13 ). The direct substitution is shown to be even more efficient for β-cyclodextrin ( 16 ), giving the heptakis (6-azido-6-deoxy)-β-CD-tetradeca (2, 3)acetate ( 17 ), while the indirect strategy fails. The compounds are characterized by extensive use of 13C- and 1H-NMR. spectroscopy. The steric and statistical problems of selective polysubstitution reactions for the cyclodextrins are discussed, and possible reasons for the observed differences in reactivity between α- and β-cyclodextrins are examined. The dodecabenzoate 3 presents a very marked solvent effect on physical properties (IR. and NMR. spectra, optical rotation); the effects observed may be ascribed to an unusually strong intramolecular network of hydrogen bonds which severely distorts the α-cyclodextrin ring and lowers the symmetry from six-fold to three-fold. 相似文献