Aliphatic Ketone Claisen Rearrangement: Troubleshooting the Transetherification Step by Identifying a Stable Acid Catalyst

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A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä

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en

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6

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Chemistry: A European Journal, Volume 30, issue 53

Abstract

After optimization for retention of catalytic activity, 4-chlorobenzoic acid emerged as the optimal catalyst for the aliphatic ketone Claisen rearrangement. The optimal catalyst enables a one-pot, metal-free, catalytic protocol from allylic alcohols to γ,δ-unsaturated ketones. The optimized process tolerates a range of substrates, including substituents with acid-labile protecting groups. Reaction monitoring and DFT studies of the aliphatic ketone Claisen process agree that the ultimate rearrangement step typically has the highest activation barrier.

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Publisher Copyright: © 2024 The Author(s). Chemistry - A European Journal published by Wiley-VCH GmbH.

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Bruce, V K, Farshadfar, K, Rolig, A, Laasonen, K & Pihko, P M 2024, 'Aliphatic Ketone Claisen Rearrangement: Troubleshooting the Transetherification Step by Identifying a Stable Acid Catalyst', Chemistry: A European Journal, vol. 30, no. 53, e202402371. https://doi.org/10.1002/chem.202402371