Regioselective Chromatic Orthogonality with Light‐Activated Metathesis Catalysts

The ability to selectively guide consecutive chemical processes towards a preferred pathway by using light of different frequencies is an appealing concept. Herein we describe the coupling of two photochemical reactions, one the photoisomerization and consequent activation of a sulfur‐chelated laten...

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Bibliographic Details
Published in:Angewandte Chemie 2015-10, Vol.127 (42), p.12561-12565
Main Authors: Levin, Efrat, Mavila, Sudheendran, Eivgi, Or, Tzur, Eyal, Lemcoff, N. Gabriel
Format: Article
Language:English
Subjects:
Activation
Catalysis
Catalysts
Chemistry
Chromatische Orthogonalität
Cyclisierungen
Decomposition reactions
Formations
Heterocyclen
Joining
Light
Metathesis
Olefinmetathese
Orthogonality
Photochemie
Wavelengths
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Summary:The ability to selectively guide consecutive chemical processes towards a preferred pathway by using light of different frequencies is an appealing concept. Herein we describe the coupling of two photochemical reactions, one the photoisomerization and consequent activation of a sulfur‐chelated latent olefin‐metathesis catalyst at 350 nm, and the other the photocleavage of a silyl protecting group at 254 nm. Depending on the steric stress exerted by a photoremovable neighboring chemical substituent, we demonstrate the selective formation of either five‐ or six‐membered‐ring frameworks by light‐triggered ring‐closing metathesis. The orthogonality of these light‐induced reactions allows the initiation of these processes independently and in interchangeable order, according to the wavelength of light used to promote them. Wellenlängenabhängig: Ein lichtaktivierbarer Olefinmetathesekatalysator und eine photospaltbare Silylschutzgruppe wurden genutzt, um zwei orthogonale Reaktionswege für die selektive Synthese von fünf‐ oder sechsgliedrigen Heterocyclen zu steuern. Welches Produkt entsteht – ein Dihydropyran oder ein Dihydrofuran —, hängt von der Reihenfolge der Lichteinstrahlung ab (siehe Schema).
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.201500740