Selective Cross‐Metathesis Versus Ring‐Closing Metathesis of Terpenes, Taking the Path Less Travelled

A diiodo ruthenium olefin metathesis pre‐catalyst was employed to achieve remarkably selective cross‐metathesis reactions of prenylated 1,6‐dienes, effectively overcoming the entropically favored intramolecular ring‐closing metathesis. This reaction was investigated using Density Functional Theory (...

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Published in:Angewandte Chemie International Edition 2024-12, Vol.63 (52), p.e202412430-n/a
Main Authors: Iudanov, Keren, Nechmad, Noy B., Poater, Albert, Lemcoff, N. Gabriel
Format: Article
Language:English
Subjects:
cross-metathesis
Density functional theory
Dienes
iodide ligands
Metathesis
Natural products
olefin metathesis
Ruthenium
sulfur-chelated ruthenium
Terpenes
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creator Iudanov, Keren
Nechmad, Noy B.
Poater, Albert
Lemcoff, N. Gabriel
description A diiodo ruthenium olefin metathesis pre‐catalyst was employed to achieve remarkably selective cross‐metathesis reactions of prenylated 1,6‐dienes, effectively overcoming the entropically favored intramolecular ring‐closing metathesis. This reaction was investigated using Density Functional Theory (DFT) computations and fine‐tuned through the application of a Design of Experiments (DoE) approach. The potential of this innovative process was demonstrated through the unprecedented functionalization of various terpene natural products via cross‐metathesis, resulting in the synthesis of new derivatives in a single step. 1,6‐Heptadiene substrates readily ring‐close to form thermodynamically stable five‐membered rings in the presence of metathesis catalysts. However, the unique selectivity displayed by Ru−SCF3−I provides a distinct cross‐metathesis pathway with various prenylated 1,6‐heptadienes, including terpenes. This new methodology presents a promising opportunity for the modification of biologically active compounds.
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source Wiley:Jisc Collections:Wiley Read and Publish Open Access 2024-2025 (reading list)
subjects cross-metathesis
Density functional theory
Dienes
iodide ligands
Metathesis
Natural products
olefin metathesis
Ruthenium
sulfur-chelated ruthenium
Terpenes
title Selective Cross‐Metathesis Versus Ring‐Closing Metathesis of Terpenes, Taking the Path Less Travelled
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