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Synthesis 2025; 57(21): 3205-3210
DOI: 10.1055/a-2626-6825
DOI: 10.1055/a-2626-6825
Paper
Halide-Substituted Grubbs–Hoveyda Catalysts for Aqueous Ring-Closing Metathesis
Authors
Supported by: German Federal Ministry of Education and Research (BMBF)
Funding Information We acknowledge the Bioökonomie REVIER_INNO PlastiQuant (FKZ:031B0918E) and the German Federal Ministry of Education and Research (BMBF) for financial support.
Dedication
This paper is dedicated to Professor Paul Knochel on the occasion of his 70th birthday.
Abstract
The effect of halide substitution in ionic-substituted second-generation Grubbs–Hoveyda catalysts (GHII catalysts, AquaMet®) on the ring-closing metathesis activity toward N,N-diallyltosylamide in aqueous media was studied by varying the reaction conditions of biological relevance (pH, buffer, salt additives). The activity, as determined by GC–MS analysis, followed the order: bromide > chloride > iodide. The robustness of these complexes, as judged by time-resolved UV–vis absorptions, followed the reverse order: iodide > chloride > bromide. Diiodide-substituted GHII catalysts performed better than the dichloride and dibromide in the ring-closing metathesis of (N-alkenyl)(N-allyl)tosylamides in aqueous buffer solutions. Catalyst decomposition by hydrolysis appears to be suppressed for the diiodo GHII catalyst in aqueous buffer solutions.
Keywords
Alkenes - Carbene complexes - Cyclization - Heterocycles - Homogeneous catalysis - MetathesisPublication History
Received: 06 May 2025
Accepted after revision: 03 June 2025
Accepted Manuscript online:
03 June 2025
Article published online:
23 July 2025
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