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Updated: Jun 2, 2026
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Cercosporin-Photocatalyzed [4+1]- and [4+2]-Annulations of Azoalkenes Under Mild Conditions
Published on: July 17, 2020
Chirogenic [3 + 2]-photocycloaddition reactions of 2-substituted naphthoquinones with cyclic alkenes
Christiane Müller1, Andreas Bauer, Thorsten Bach
1Lehrstuhl für sOrganische Chemie I, Technische Universität München, Garching, Germany.
Abstract:
The formal [3 + 2]-photocycloaddition of 2-hydroxy- (2a) and 2-amino-1,4-naphthoquinone (2b) to olefins was studied in various solvents aiming at a possible enantioselective reaction course. The reaction conditions were optimised for irradiation at low temperature in a nonpolar solvent employing external fluorescent lamps as irradiation sources. Best yields for the reaction of 2-hydroxy-1,4-naphthoquinone (2a) with 1-methyl-2-butene were obtained when using a large excess of the olefin (200 equiv.) in toluene as the solvent at an irradiation wavelength of λ = 419 nm. Under these conditions a variety of cyclic alkenes (cyclopentene, cyclohexene, dihydropyran, 1-methylcyclohex-1-ene) underwent the photocycloaddition in yields of 22-84%. Reactions with 2-hydroxy-1,4-naphthoquinone (2a) could be performed enantioselectively at -60 °C in toluene as the solvent employing a chiral hydrogen bonding template. The enantiomeric excess (≤11%) remained low, however. Possible reasons for this lack of selectivity are discussed.
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Electrophilic Addition to Alkynes: Halogenation
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.