Infoscience

Journal article

Fluoronaphthalene building blocks via arynes: A solution to the problem of positional selectivity

When 3-fluoro- and 3-chloro-1,2-didehydrobenzenes are generated in the presence of 2-(trimethylsilyl)furan, two regioisomeric cycloadducts are formed in a 1:2 ratio. However, regioselectivity can be installed by fitting one bulky trimethylsilyl group into sterically crit. positions of each of the two reaction components. Thus 3-fluoro-6-trimethylsilyl-1,2-didehydrobenzene and 2-(trimethylsilyl)furan give one cycloadduct exclusively. In this way, the Diels-Alder reaction between suitably adorned arynes and similarly designed furans can open an entry to naphthalene derivs. that have unprecedented substituent patterns that qualify them as building blocks for pharmaceutical or agricultural research. The acid-catalyzed isomerization of model 1,4-epoxy-1,4-dihydronaphthalenes, the aryne/furan cycloadducts, exhibits unexpected effects on rates and regioselectivity. [on SciFinder (R)]

    Keywords: Isomerization (acid-catalyzed epoxide ring opening/isomerization; regioselective acid-catalyzed ring-opening/isomerization of epoxynaphthalene derivs.); Alkynes; Aromatic hydrocarbons Role: RCT (Reactant) ; SPN (Synthetic preparation) ; PREP (Preparation) ; fluoronaphthalene regioselective Diels Alder cycloaddn prepn aryne furan benzyne; trimethylsilyl group steric hindrance regioselective Diels Alder cycloaddn; naphthol prepn epoxydihydronaphthalene ring opening isomerization acid catalyst; epoxydihydrona

    Note:

    CAN 144:69609 25-24 Benzene, Its Derivatives, and Condensed Benzenoid Compounds Institute of Chemical Sciences and Engineering,Ecole Polytechnique Federale (BCh),Lausanne,Switz. Journal 1434-193X written in English. 871824-08-7P; 871824-09-8P Role: PNU (Preparation, unclassified), PREP (Preparation) (failed prepn. of trimethylsilyl fluoronaphthols via acid-catalyzed ring-opening of 1,4-epoxy-1,4-dihydro-5-fluoro-8-(trimethylsilyl)naphthalene); 871824-06-5P; 871824-07-6P Role: PNU (Preparation, unclassified), PREP (Preparation) (failed prepn. of trimethylsilyl naphthols via acid-catalyzed ring-opening of 1,4-epoxy-1,4-dihydro-5-(trimethylsilyl)naphthalene); 871824-01-0P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. of fluoronaphthalene derivs. via regioselective Diels-Alder cycloaddns. of arynes and furans, and failed reactant of acid-catalyzed ring-opening); 75-77-4 (Chlorotrimethylsilane); 110-00-9 (Furan); 372-18-9 (1,3-Difluorobenzene); 462-06-6 (Fluorobenzene); 541-73-1 (1,3-Dichlorobenzene); 110407-59-5 Role: RCT (Reactant), RACT (Reactant or reagent) (prepn. of fluoronaphthalene derivs. via regioselective Diels-Alder cycloaddns. of arynes and furans, and reaction rates and regioselectivity of acid-catalyzed ring-opening of epoxynaphthalene derivs.); 1578-33-2P (2-Trimethylsilylfuran); 1842-26-8P; 731799-14-7P; 871824-00-9P; 871824-05-4P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. of fluoronaphthalene derivs. via regioselective Diels-Alder cycloaddns. of arynes and furans, and reaction rates and regioselectivity of acid-catalyzed ring-opening of epoxynaphthalene derivs.); 90-15-3P (1-Naphthol); 61761-32-8P; 134965-26-7P; 134965-27-8P; 383155-01-9P; 871824-02-1P; 871824-03-2P; 871824-04-3P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. of fluoronaphthalene derivs. via regioselective Diels-Alder cycloaddns. of arynes and furans, and reaction rates and regioselectivity of acid-catalyzed ring-opening of epoxynaphthalene derivs.); 573-57-9 Role: RCT (Reactant), RACT (Reactant or reagent) (ref. compd. to calc. reaction rates of acid-catalyzed ring-opening of epoxynaphthalene derivs.)

    Reference

    Record created on 2006-03-03, modified on 2016-08-08

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