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Synthesis of alkylidenephthalans through fluoride-induced cyclization of electron-deficient 2-siloxymethylphenylacetylene derivatives.

ABSTRACT: Fluoride-based deprotection of silylated 2-alkynylbenzyl alcohol derivatives featuring carbonyl-substituted alkynes results in the direct synthesis of alkylidenephthalan vinylogous esters. The reaction is selective for the Z alkylidenephthalans in a thermodynamically controlled process. Similar compounds are also produced in the coupling of Fischer carbene complexes with 2-alkynylbenzoyl derivatives in an aqueous solvent system. Subsequent acid-catalyzed inter- or intramolecular Diels-Alder reactions lead to hydronaphthalene or hydrophenanthrene derivatives.

SUBMITTER: Duan S

PROVIDER: S-EPMC1868474 | biostudies-literature | 2007 Apr

REPOSITORIES: biostudies-literature

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Synthesis of alkylidenephthalans through fluoride-induced cyclization of electron-deficient 2-siloxymethylphenylacetylene derivatives.

Duan Shaofeng S Cress Karen K Waynant Kris K Ramos-Miranda Elias E Herndon James W JW

Tetrahedron 20070401 14

Fluoride-based deprotection of silylated 2-alkynylbenzyl alcohol derivatives featuring carbonyl-substituted alkynes results in the direct synthesis of alkylidenephthalan vinylogous esters. The reaction is selective for the Z alkylidenephthalans in a thermodynamically controlled process. Similar compounds are also produced in the coupling of Fischer carbene complexes with 2-alkynylbenzoyl derivatives in an aqueous solvent system. Subsequent acid-catalyzed inter- or intramolecular Diels-Alder reac ...[more]

PMID: 18382602

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Project description:Rapid and efficient analysis of fluoride ion is crucial to providing key information for fluoride ion hazard assessment and pollution management. In this study, we synthesized one symmetrical structure called 1,4-bis(4,5-diphenyl-1H-imidazol-2-yl)benzene (1a) and two asymmetrical structures, namely 2-(4-(4,5-diphenyl-1H-imidazol-2-yl)phenyl)-1H-phenanthro(9,10-d)imidazole (1b) and 2-(4-(4,5-diphenyl-1H-imidazol-2-yl)phenyl)-1H-imidazo(4,5-f)(1,10)phenanthroline (1c), which served as an efficient anion sensor for fluoride ion over a wide range of other anions (Cl-, Br-, I-, NO₃-, ClO₄-, HSO₄-, BF₄-, and PF₆-) owing to imidazole group in the main backbone. The absorption intensity of compound 1a at λmax 358 nm slightly decreased; however, a new band at λmax 414 nm appeared upon the addition of fluoride ion, while no evident change occurred upon the addition of eight other anions. The photoluminescence intensity of compound 1a at λmax 426 nm was nearly quenched and fluorescence emission spectra were broadened when fluoride ion was added into dimethyl sulfoxide (DMSO) solution of compound 1a. Compared with the optical behaviors of the DMSO solution of compound 1a in the presence of Bu₄N⁺F-, compounds 1b and 1c exhibited considerable sensitivity to fluoride ion due to the increase in coplanarity. Furthermore, compared with the fluorescence emission behaviors of the DMSO solutions of compounds 1a and 1b in the presence of Bu₄N⁺F-, compound 1c exhibited the most significant sensitivity to fluoride ion due to the charge transfer enhancement. Consequently, the detection limits of compounds 1a-1c increased from 5.47 × 10-6 M to 4.21 × 10-6 M to 9.12 × 10-7 M. Furthermore, the largest red shift (75 nm) of the DMSO solution compound 1c in the presence of fluoride ion can be observed. Our results suggest that the increase in coplanarity and the introduction of electron-withdrawing groups to the imidazole backbone can improve the performance in detecting fluoride ion.

Dataset Information

Synthesis of alkylidenephthalans through fluoride-induced cyclization of electron-deficient 2-siloxymethylphenylacetylene derivatives.

Publications

Synthesis of alkylidenephthalans through fluoride-induced cyclization of electron-deficient 2-siloxymethylphenylacetylene derivatives.

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