1. A New Insight into the Stereoelectronic Control of the Pd-0-Catalyzed Allylic Substitution: Application for the Synthesis of Multisubstituted Pyran-2-ones via an Unusual 1,3-Transposition
- Author
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Zbyněk Brůža, Jiří Kuneš, Lubomír Rulíšek, Jeremy N. Harvey, Jiří Kratochvíl, Milan Pour, Jana Maříková, Lucie Nováková, and Pavel Kočovský
- Subjects
Allylic rearrangement ,Stereochemistry ,Chemistry, Multidisciplinary ,Kinetics ,chemistry.chemical_element ,010402 general chemistry ,01 natural sciences ,Quantum chemistry ,Catalysis ,chemistry.chemical_compound ,OXIDATIVE ADDITION ,Alkane stereochemistry ,Carboxylate ,SYN-ANTI DICHOTOMY ,quantum chemistry calculations ,CIS ,Science & Technology ,INTRAMOLECULAR 1,2 SHIFTS ,catalysis ,010405 organic chemistry ,Organic Chemistry ,stereoelectronic effects ,General Chemistry ,CORRELATION-ENERGY ,palladium ,allylic rearrangement ,0104 chemical sciences ,Chemistry ,STEREOCHEMICAL INHIBITION ,chemistry ,CONVENIENT SYNTHESIS ,Pyran ,Physical Sciences ,CROSS-COUPLING REACTIONS ,ASYMMETRIC ALLYLATION ,COMPLEXES ,Palladium - Abstract
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. ispartof: CHEMISTRY-A EUROPEAN JOURNAL vol:25 issue:34 pages:8053-8060 ispartof: location:Germany status: published
- Published
- 2019