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Master of Science (MS)
Vyvyan, James R.
Clark, Timothy B. (Chemist)
Gold catalyzed reactions are an active area of interest for synthetic chemists due to gold's ability to promote formation of carbon-carbon bonds. A mechanistic study of the aromatic Claisen rearrangement of allyl aryl ethers in the presence of a gold catalyst has shed some light on the role of the gold catalyst in this reaction. Studies probing the electronics requirements of the reaction as well as investigation of stereochemical conservation both support a dissociative ionic mechanism. Our data supports that the catalyst interacts primarily with the alkene branch as opposed to the phenoxide oxygen because the E and Z allyl aryl ether diastereomers form different ratios of the [3,3] and [1,3] rearrangement products. NMR studies have caused us to question our presumed active catalyst, Ph3PAuOTf, and we now suspect gold nanoparticles or a thin gold film are catalyzing the rearrangement. Through investigations of the synthetic scope of our gold catalyst, some unexpected reaction products were produced. A cyclic ether formed when the allyl branch contained an acetonide protecting group. This cyclization was even more effective when the acetonide was first converted to the corresponding diol. This cyclic ether formation was put to practical use in the total synthesis of the natural product (±)-centrolobine.
Catalysts--Synthesis, Claisen rearrangement
Western Washington University
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Dimmitt, Heidi E., "Gold(I)-catalyzed rearrangements of allyl aryl ethers: mechanisitc and synthetic studies" (2011). WWU Graduate School Collection. 112.