Preparation, Properties, and Uses of Benzeneboronic Acid

Washburn, Robert M.; Levens, Ernest; Albright, Charles F.; Billig, Franklin A.; Cernak, E. S.

doi:10.1021/ba-1959-0023.ch011

Cited by 19 publications

(4 citation statements)

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“…On the basis of this study, we envisaged analogous reaction between arylboronic acids and 2-bromo-5-methoxybenzaldehyde as the key step in planning our strategy for the synthesis of 3-hydroxybenzo[ c ]phenanthrene ( 5 ) and 12-hydroxybenzo[ g ]chrysene ( 6 ) (see Scheme ). The required boronic acids, naphthalene-1-boronic acid ( 7 ) and phenanthrene-9-boronic acid ( 8 ), and 2-bromo-5-methoxybenzaldehyde ( 9 ) were readily accessible according to the literature procedures. Thus, the coupling reaction of 7 or 8 with 9 in the presence of anhydrous CsF and a catalytic amount of Pd(PPh 3 ) 4 produced 10 or 11 in nearly quantitative yield (96−100%).…”

Section: Resultsmentioning

confidence: 99%

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

Kumar

1997

J. Org. Chem.

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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 61-64% 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.

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Section: Resultsmentioning

confidence: 99%

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

Kumar

1997

J. Org. Chem.

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“…The basis for this selection is the oxidative and hydrolytic stability of the aryl carbon-boron bond and the demonstration of its metabolic inertness. 85,86 Among the first generation boron-containing compounds for BNCT, p-carboxyphenylboronic acid (PCPB) 87 and Na 2 B 10 H 10 88 had been evaluated, however, without much success. In the process of searching for better BNCT agents, sodium mercaptoundecahydrododecaborate (Na 2 B 12 H 11 SH, BSH) 89 and 4-dihydroxyborylphenylalanine (BPA) 90 were selected for biological evaluation.…”

Section: Figure 11mentioning

confidence: 99%

Boronic acid compounds as potential pharmaceutical agents

Yang

Gao

Wang

2003

Medicinal Research Reviews

464

289

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Boronic acid compounds have been used, because of their unique structural features, for the development of potent enzyme inhibitors, boron neutron capture agents for cancer therapy, and as antibody mimics that recognize biologically important saccharides. Consequently, there has been a surge of interests in boronic acid compounds. This study reviews the recent development in this area during the last six years.

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“…RBBr2-SMe2 + 2H20 -RB(OH)2 + 2HBr (6) Thus, a solution of alkyldibromoborane-dimethyl sulfide in methylene chloride, when added to a mixture of water (excess) and ethyl ether, is converted rapidly and quantitatively into the corresponding boronic acid. The HBr liberated remains in the aqueous layer.…”

Section: Resultsmentioning

confidence: 99%