Proximity effects in peri-substituted naphthalenes. I. Some 8-substituted 1-(hydroxymethyl)- and 1-(chloromethyl)naphthalenes

Kleinfelter, Donald C.; Chen, Paul H.

doi:10.1021/jo01258a047

Cited by 12 publications

(4 citation statements)

References 1 publication

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“…In view of the geometry of naphthalene, substituents located at these positions are in much closer proximity than similar substituents located ortho to each other, and steric interactions should be more severe. This closer proximity has been responsible for the appearance of several unique properties of peri -substituted naphthalenes that have been reported by different groups over many years ( − ).…”

Section: Discussionmentioning

confidence: 77%

Importance of peri-Interactions on the Stereospecificity of Rat Hydroxysteroid Sulfotransferase STa with 1-Arylethanols

Banoğlu

Duffel

1999

Chem. Res. Toxicol.

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Hydroxysteroid (alcohol) sulfotransferases catalyze the sulfation of polycyclic aromatic hydrocarbons (PAHs) that contain benzylic hydroxyl functional groups. This metabolic reaction is often a critical step in the activation of a hydroxyalkyl-substituted PAH to form an electrophilic metabolite that is capable of forming covalent bonds at nucleophilic sites on DNA, RNA, and proteins. Since hydroxyalkyl-substituted PAHs are often metabolically formed by the stereoselective enzymatic hydroxylation of a benzylic position on an alkyl-substituted PAH, we have investigated the possibility that the sulfation of hydroxyalkyl aromatic hydrocarbons is also stereoselective. Homogeneous preparations of rat hepatic hydroxysteroid (alcohol) sulfotransferase STa were utilized to investigate the stereoselectivity of its catalytic function with the enantiomers of model 1-arylethanols. While only minimal stereoselectivity was observed for the catalytic efficiency of STa with the enantiomers of 1-(2-naphthyl)ethanol and 1-acenaphthenol, the enzyme was stereospecific for (R)-(+)-1-(1-naphthyl)ethanol, (R)-(+)-1-(1-pyrenyl)ethanol, and (R)-(+)-1-(9-phenanthryl)ethanol as substrates. Moreover, (S)-(-)-1-(1-naphthyl)ethanol, (S)-(-)-1-(1-pyrenyl)ethanol, and (S)-(-)- 1-(9-phenanthryl)ethanol were competitive inhibitors of STa. Structural and conformational analyses of these 1-arylethanols indicated that steric interactions between the substituents on the benzylic carbon and the hydrogen in the peri-position on the aromatic ring system were important determinants of the stereospecificity of the enzyme with these molecules. The findings presented here have implications for the more accurate prediction of the ability of hydroxyalkyl-substituted PAHs to be activated via metabolic formation of electrophilic sulfuric acid esters.

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Section: Discussionmentioning

confidence: 77%

Importance of peri-Interactions on the Stereospecificity of Rat Hydroxysteroid Sulfotransferase STa with 1-Arylethanols

Banoğlu

Duffel

1999

Chem. Res. Toxicol.

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“…The mixture was poured on ice and extracted with AcOEt (3 Â 50 ml), the combined org. phase washed with ice water (5 Â) to remove the diglyme, dried (Na 2 SO 4 ), and evaporated, and the crude product purified by CC (SiO 2 (22 g), 2.5 Â 15 cm; toluene/AcOEt 9 : [60] and (5-Nitronaphthalen-1-yl)methanol. Under Ar and under cooling, 8-nitronaphthalene-1-carboxylic acid (109)/5-nitronaphthalene-1-carboxylic acid 5 : 1 [75] (7.1 g, 33 mmol) was added to a suspension of NaBH 4 (1.9 g, 50 mmol) in diglyme (55 ml).…”

Section: -Ethyl-3-nitrobenzenaminementioning

confidence: 99%

“…Diborane reduction of (8-nitro-1-naphthyl)acetic acid (106) [58] on the other hand led to 105. The isomeric 1-(8-nitro-1-naphthyl)ethanol (108) resulted from the reduction of 8-nitro-1-acetonaphthone (107) [59], and (8-nitro-1-naphthyl)methanol (110) [60] was synthesized from Scheme 1 8-nitro-naphthalene-1-carboxylic acid (109) by treatment with diborane. The (1-nitro-2-naphthyl)methanol (113) was prepared from 2-methyl-1-nitronapthalene (100) by monobromination to the 2-(bromomethyl) derivative 111, followed by substitution with AcOK to give the 2-[(acetyloxy)methyl] compound 112 and subsequent hydrolysis.…”

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confidence: 99%

New Types of Very Efficient Photolabile Protecting Groups Based upon the [2‐(2‐Nitrophenyl)propoxy]carbonyl (NPPOC) Moiety

Bühler

Lagoja

Giegrich

et al. 2004

Helvetica Chimica Acta

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Based upon the photolabile [2-(2-nitrophenyl)propoxy]carbonyl group (NPPOC), a large number of modified 2-(2-nitrophenyl)propanol derivatives substituted at the phenyl ring (see 23 ± 34 and 57 ± 76) as well as at the side-chain (see 85 ± 92 and 95 ± 98) were synthesized to improve the photoreactivity of this new type of photolabile entity. The phenyl moiety was also exchanged by the naphthalenyl group (see 102, 103, 105, 108, 110, 113, and 114), the thienyl substituent (see 115, 117, 118, and 120), and the benzothienyl substituent (see 121). The 2-(2-nitroaryl-and heteroaryl)propanols were converted with diphosgene into the corresponding carbonochloridates, which reacted subsequently with thymidine to the thymidine 5'-(protected carbonates) 123 ± 178 as the main reaction products. In several cases, the corresponding 3'-carbonates and 3',5'-dicarbonates 179 ± 212 were also isolated and characterized. Photolysis studies under standardized conditions (see Table) indicated that the rate of photocleavage varies in a broad range depending on the substituents. So far, thepropyl carbonates] 141 and 142, and 5'-[2-(2-nitro-5-thienylphenyl)propyl carbonates] 143 and 144 showed the best properties regarding fast and uniform deprotection. Since the nucleobases of 213 ± 215 do not influence the photocleavage features, in general, the new type of photolabile building blocks allows in form of their 3'-phosphoramidites the photolithographic formation of high-quality biochips.

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“…The reaction mixture was stirred for 30 min and cooled to −78C. After 5 min 8-(hydroxymethyl)naphth-1-yl methyl ether ( 6 ) (1.0 g, 5.32 mmol) in dry dichloromethane (20 mL) was added (dropwise over 5−10 min). After 10 min TEA (2.15 g, 0.02 mol) was added.…”

Section: Methodsmentioning

confidence: 99%

Selective Synthesis of meso-Naphthylporphyrins

Cammidge

Öztürk

2002

J. Org. Chem.

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A series of novel meso-(8-substituted naphth-1-yl)porphyrins has been synthesized creating derivatives with a tight recognition environment above the porphyrin plane. The selective synthesis of single atropisomers is discussed. Condensation of bisnaphthaldehyde 12 with phenyldipyrromethane unexpectedly led to selective synthesis of the alpha,alpha-5,10-bridged isomer 14. A mechanism is proposed for this unusual scrambling, and alternative syntheses of alpha,alpha-5,15-bisnaphthylporphyrins are described. Synthesis of 5,15-analogues can be achieved by employing (pentafluorophenyl)dipyrromethane or via presynthesis of a bis(dipyrromethane) derivative 22 (from bisnaphthaldehyde 12) and subsequent condensation with benzaldehyde.

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Proximity effects in peri-substituted naphthalenes. I. Some 8-substituted 1-(hydroxymethyl)- and 1-(chloromethyl)naphthalenes

Cited by 12 publications

References 1 publication

Importance of peri-Interactions on the Stereospecificity of Rat Hydroxysteroid Sulfotransferase STa with 1-Arylethanols

Importance of peri-Interactions on the Stereospecificity of Rat Hydroxysteroid Sulfotransferase STa with 1-Arylethanols

New Types of Very Efficient Photolabile Protecting Groups Based upon the [2‐(2‐Nitrophenyl)propoxy]carbonyl (NPPOC) Moiety

Selective Synthesis of meso-Naphthylporphyrins

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