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A New Insight into the Stereoelectronic Control of the Pd0-Catalyzed Allylic Substitution: Application for the Synthesis of Multisubstituted Pyran-2-ones via an Unusual 1,3-Transposition

Journal Contribution - Journal Article

Pyran-2-ones 3 undergo a novel Pd0 -catalyzed 1,3-rearrangement to afford isomers 6. The reaction proceeds via an η2 -Pd complex, the pyramidalization of which (confirmed by quantum chemistry calculations) offers a favorable antiperiplanar alignment of the Pd-C and allylic C-O bonds (C), thus allowing the formation of an η3 -Pd intermediate. Subsequent rotation and rate-limiting recombination with the carboxylate arm then gives isomeric pyran-2-ones 6. The calculated free energies reproduce the observed kinetics semi-quantitatively.
Journal: Chemistry - a European Journal
ISSN: 0947-6539
Issue: 34
Volume: 25
Pages: 8053 - 8060
Publication year:2019
BOF-keylabel:yes
IOF-keylabel:yes
BOF-publication weight:1
CSS-citation score:1
Authors:International
Authors from:Higher Education
Accessibility:Open