- Synthesis of dibenzo[def,p]chrysene, its active metabolites, and their 13C-labeled analogues
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Dibenzo[def,p]chrysene (DBC) Is a highly carcinogenic polycyclic aromatic hydrocarbon suspected to be Involved in initiation of lung cancer in smokers. Efficient new syntheses of DBC, Its active metabolites [DBC diol (1), DBC dione (2), DBC diol epoxlde (3)], and their previously unknown 13C 2-labeled analogues are reported. The 13C 2-labeled analogues are required as standards for sensitive methods of analysis of their DNA adducts in human cells using stable isotope dilution liquid chromatography/tandem mass spectrometry.
- Xu, Daiwang,Duan, Yazhen,Blair, Ian A.,Penning, Trevor M.,Harvey, Ronald G.
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supporting information; experimental part
p. 1059 - 1062
(2009/04/06)
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- Microwave-assisted suzuki cross-coupling reaction, a key step in the synthesis of polycyclic aromatic hydrocarbons and their metabolites
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(Chemical Equation Presented) A highly efficient and general method for Suzuki cross-coupling reaction en route to the synthesis of polycyclic aromatic hydrocarbons (PAHs) and their metabolites has been developed. Microwave irradiation of aryl bromides 1
- Sharma, Arun K.,Gowdahalli, Krishnegowda,Krzeminski, Jacek,Amin, Shantu
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p. 8987 - 8989
(2008/03/12)
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- A New and Concise Synthesis of 3-Hydroxybenzo[c]phenanthrene and 12-Hydroxybenzo[g]chrysene, Useful Intermediates for the Synthesis of Fjord-Region Diol Epoxides of Benzo[c]phenanthrene and Benzo[g]chrysene
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A new strategy which involves a palladium-catalyzed cross-coupling reaction has been developed for the rapid synthesis of 3-hydroxybenzo[c]phenanthrene (5) and 12-hydroxybenzo[g]chrysene (6). These phenolic compounds are the key intermediates for the synthesis of highly carcinogenic fjord-region diol epoxide metabolites 3 and 4 of benzo[c]phenanthrene (1) and benzo[g]chrysene (2). The cross-coupling reaction of 2-bromo-5-methoxybenzaldehyde (9) with naphthalene-1-boronic acid (7) and phenanthrene-9-boronic acid (8) produced 2-(1-naphthyl)-5-methoxybenzaldehyde (10) and 2-(9-phenanthryl)-5-methoxybenzaldehyde (11), respectively, in quantitative yields. After reaction of these aldehydes with trimethylsulfonium iodide under phase-transfer conditions or with the Wittig reagent obtained from (methoxymethyl)triphenylphosphonium bromide and phenyllithium to generate an oxiranyl or methoxyethene side chain, the acid-catalyzed cyclization with methanesulfonic acid (or boron trifluoride) produced 3-methoxybenzo[c]phenanthrene (16) and 12-methoxybenzo[g]chrysene (17) in 61-64percent yields. Finally, demethylation of these methoxy derivatives 16 and 17 with boron tribromide resulted in the formation of the hydroxy analogues 5 and 6, respectively. The availability of this short and high-yielding regiospecific method for the synthesis of phenols 5 and 6 should allow the preparative-scale synthesis of the fjord-region diol epoxides 3 and 4. These diol epoxides are required as starting compounds for the synthesis of site-specifically modified oligonucleotides which are critically needed to elucidate the mechanism of carcinogenesis at the molecular level.
- Kumar, Subodh
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p. 8535 - 8539
(2007/10/03)
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