Reaction pathways leading to arylene ethynylene macrocycles via alkyne metathesis

Abstract

Mechanistic studies on the direct formation of arylene ethynylene macrocycles via alkyne metathesis catalyzed by a molybdenum complex are reported. Gel permeation chromatography (GPC) and matrix-assisted laser desorption ionization (MALDI) mass spectrometry on the products from metathesis of monomer 1 show the initial formation of linear oligomers and large macrocycles (n > 6), followed by their transformation into the thermodynamically most stable product distribution-mainly the cyclic hexamer. Variable temperature and scrambling experiments reveal the reversibility of macrocycle formation. Nearly identical product distributions are observed from the cross metathesis of hexacycle 2 with diphenylacetylene and from the metathesis of bis(phenylethynyl) substituted monomer 4, demonstrating that macrocycle formation is thermodynamically rather than kinetically controlled. The metathesis byproduct, 3-hexyne, is shown to inhibit the catalyst. It is suggested that the relative metathesis rates of dialkylalkynes versus diarylalkynes trap the catalyst in a nonproductive manifold, rendering it unavailable for the productive metathesis of aryl alkylalkyne substrates. This finding indicates that dialkyl-substituted alkyne byproducts should be avoided (or efficiently removed) if the metatheses of aryl substrates, especially those with electron-withdrawing groups, are to proceed to high conversion.