Regioselective Chromatic Orthogonality with Light-Activated Metathesis Catalysts

Efrat Levin, Sudheendran Mavila, Or Eivgi, Eyal Tzur, N. Gabriel Lemcoff

Research output: Contribution to journalArticlepeer-review

30 Scopus citations

Abstract

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 350nm, and the other the photocleavage of a silyl protecting group at 254nm. 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. A guiding light: By the combination of a light-activated sulfur-chelated olefin-metathesis catalyst with a photocleavable bulky silyl protecting group, two orthogonal pathways enabled the selective synthesis of five- or six-membered heterocycles according to the order in which the starting material was irradiated with light of different wavelengths. Thus, protecting-group removal and metathesis gave either a dihydropyran or a dihydrofuran.

Original languageEnglish
Pages (from-to)12384-12388
Number of pages5
JournalAngewandte Chemie - International Edition
Volume54
Issue number42
DOIs
StatePublished - 1 Oct 2015

Keywords

  • chromatic orthogonality
  • cyclization
  • heterocycles
  • olefin metathesis
  • photochemistry

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