Facile regio- and stereoselective total synthesis of racemic aklavinone

Li, Tsung Tee; Wu, Yu Lin

doi:10.1021/ja00413a059

Cited by 64 publications

(5 citation statements)

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“…Later, it was observed that when 51 was mixed with AlCl 3 at room temperature, a slow reaction occurred to give 59 cleanly. Optimized reaction conditions for the selective cleavage of the methyl ether in the presence of the methyl ester in 51 involve reacting 51 and AlCl 3 in refluxing CH 2 Cl 2 48,49 (eq 1). The desired product 59 was obtained in 93% yield by this method.…”

Section: Resultsmentioning

confidence: 99%

Total Synthesis of Dimethyl Sulfomycinamate

Kelly

Lang

1996

J. Org. Chem.

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Dimethyl sulfomycinamate (1), a methanolysis product from the natural antibiotic sulfomycin I, is synthesized in 11 steps (Scheme 19). The chemistry of various pyridine, thiazole, and oxazole heterocycles and their coupling reactions under palladium catalysis are examined. The key transformations in the synthesis are the selective palladium-catalyzed coupling reactions on doubly activated pyridine 62 and the condensation reaction between bromo ketone 69 and amide 28 to form the oxazole moiety 76. The first preparation of oxazole triflates is described, as are some of their chemical properties.

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Section: Resultsmentioning

confidence: 99%

Total Synthesis of Dimethyl Sulfomycinamate

Kelly

Lang

1996

J. Org. Chem.

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“…The alcohol group of compound 3a was then replaced by fluoride directly using (diethylamino)sulfur trifluoride (DAST) to give (2 R* ,3 S* )-5-fluoro-2,3-bis(4−methoxyphenyl)pentanenitrile ( 4a ). However, attempts to deprotect the methyl ether to give unlabeled FEDPN ( 5 ) failed to do so without also cleaving the C−F bond (Reagents including BBr 3 , , BF 3 , AlCl 3 , pyridine·HCl, , and CH 3 SO 3 H were tried under various reaction conditions.) Thus, we decided to change to a more easily cleaved protecting group.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of an Estrogen Receptor β-Selective Radioligand: 5-[¹⁸F]Fluoro-(2R,3S)-2,3-bis(4-hydroxyphenyl)pentanenitrile and Comparison of in Vivo Distribution with 16α-[¹⁸F]Fluoro-17β-estradiol

et al. 2005

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Estrogen receptor beta (ERbeta), a less active ER subtype that appears to have a restraining effect on the more active ERalpha, could be a factor that determines the level of estrogen action in certain estrogen target tissues. ERbeta is found in breast cancer, and its levels relative to ERalpha decline with disease progression. Thus, the independent quantification of ERalpha and ERbeta levels in breast cancer by imaging might be predictive of responses to different hormone therapies. To develop an imaging agent for ERbeta, we synthesized a fluoroethyl analogue of DPN (2,3-bis(4-hydroxyphenyl)propanonitrile), a known ERbeta-selective ligand. This analogue, FEDPN (5-fluoro-(2R,3S)-2,3-bis(4-hydroxyphenyl)pentanenitrile), has an 8.3-fold absolute affinity preference for ERbeta. [18F]Fluoride-labeled FEDPN was prepared from a toluenesulfonate precursor, which provided [18F]FEDPN with a specific activity greater than 3100 Ci/mmol after HPLC purification. Biodistribution studies in immature female rats using estradiol as a blocking agent revealed specific uptake of [18F]FEDPN in the uterus and ovaries. Experiments using ERalpha- and ERbeta-knockout mice demonstrated the expected ERalpha-subtype dependence in the tissue uptake of the known 16alpha-[18F]fluoro-17beta-estradiol ([18F]FES), which has a 6.3-fold preference for ERalpha. The tissue uptake of [18F]FEDPN in the ER knockout mice showed some evidence of mediation by ERbeta, but the levels of specific uptake of this agent were relatively modest. Based on our results, imaging of ERalpha can be done effectively with [18F]FES, but imaging of ERbeta will likely require agents with more optimized ERbeta binding affinity and selectivity than [18F]FEDNP.

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“…Of these antibiotics, aclacinomycin A was the subject of substantial investigation and was found to have high anticancer activity while being less toxic than the clinically useful rhodomycin, daunorubicin [ 3 – 7 ]. Because of its biological importance, there was high interest in its total synthesis [ 8 – 11 ]. Jones and Lock managed the synthesis of aklavinone via electron-deficient o-quinoid pyrones [ 12 ].…”

Section: Introductionmentioning

confidence: 99%

Tautomerism in 11-Hydroxyaklavinone: A DFT Study

Türker

2012

The Scientific World Journal

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The antharquinone-based chromophore of 11-hydroxyaklavinone is present in the structure of an anticancer agent, daunomycin. On the other hand, aklavinone is the parent aglycone of certain anthracycline antibiotics that possess anti-cancer activity too. The structures of aklavinone and its 11-hydroxy derivative have many –OH groups, and two keto groups which may take place in certain tautomeric equilibria. Of these tautomeric forms, presently the one involving the anthraquinone based tautomers of 11-hydroxyaklavinone has been investigated quantum chemically in the framework of the density functional theory at the levels of RB3LYP/6-31G(d) and RB3LYP/6-31G(d,p).

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Facile regio- and stereoselective total synthesis of racemic aklavinone

Cited by 64 publications

References 1 publication

Total Synthesis of Dimethyl Sulfomycinamate

Total Synthesis of Dimethyl Sulfomycinamate

Synthesis of an Estrogen Receptor β-Selective Radioligand: 5-[¹⁸F]Fluoro-(2R,3S)-2,3-bis(4-hydroxyphenyl)pentanenitrile and Comparison of in Vivo Distribution with 16α-[¹⁸F]Fluoro-17β-estradiol

Tautomerism in 11-Hydroxyaklavinone: A DFT Study

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Facile regio- and stereoselective total synthesis of racemic aklavinone

Cited by 64 publications

References 1 publication

Total Synthesis of Dimethyl Sulfomycinamate

Total Synthesis of Dimethyl Sulfomycinamate

Synthesis of an Estrogen Receptor β-Selective Radioligand: 5-[18F]Fluoro-(2R*,3S*)-2,3-bis(4-hydroxyphenyl)pentanenitrile and Comparison of in Vivo Distribution with 16α-[18F]Fluoro-17β-estradiol

Tautomerism in 11-Hydroxyaklavinone: A DFT Study

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Synthesis of an Estrogen Receptor β-Selective Radioligand: 5-[¹⁸F]Fluoro-(2R,3S)-2,3-bis(4-hydroxyphenyl)pentanenitrile and Comparison of in Vivo Distribution with 16α-[¹⁸F]Fluoro-17β-estradiol