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Updated: Sep 19, 2025
Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
Unlocking Chromium Decarboxylative Ligand-to-Metal Charge Transfer: Efficient and Redox-Neutral Allylation of
Supeng Wu1, Ziqi Jiao1, Alex T Sung1
1Department of Chemistry, Vanderbilt University, Nashville, Tennessee 37235, United States.
Abstract:
Here, we report the light-induced decarboxylative ligand-to-metal charge transfer (LMCT) of Cr(III) carboxylate complexes and demonstrate its applicability toward stereoselective Nozaki-Hiyama-Kishi (NHK) allylation reactions. The critical design element of our reaction was identifying a bipyridyl ligand scaffold that enables a single Cr catalyst to facilitate both photolytic dissociation and aldehyde addition. This approach allows for the direct utilization of carboxylic acids and eliminates the need for external redox reagents. The broad utility of this protocol was demonstrated by the preparation of a variety of homoallylic alcohols in good yields and diastereoselectivities as well as the identification of advantageous retrosynthetic disconnections. Extensive studies supported the LMCT mechanism of this transformation, including the characterization of the catalytically active Cr-carboxylate species.
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