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

0507868 - ÚOCHB 2020 RIV DE eng J - Článek v odborném periodiku
Brůža, Z. - Kratochvíl, J. - Harvey, J. N. - Rulíšek, Lubomír - Nováková, L. - Maříková, J. - Kuneš, J. - Kočovský, P. - Pour, M.
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.
Chemistry - A European Journal. Roč. 25, č. 34 (2019), s. 8053-8060. ISSN 0947-6539. E-ISSN 1521-3765
Institucionální podpora: RVO:61388963
Klíčová slova: allylic rearrangement * catalysis * palladium * quantum chemistry calculations * stereoelectronic effects
Obor OECD: Physical chemistry
Impakt faktor: 4.857, rok: 2019
Způsob publikování: Omezený přístup
https://onlinelibrary.wiley.com/doi/abs/10.1002/chem.201900323

Pyran-2-ones 3 undergo a novel Pd-0-catalyzed 1,3-rearrangement to afford isomers 6. The reaction proceeds via an eta(2)-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 eta(3)-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.
Trvalý link: http://hdl.handle.net/11104/0298826