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Molecules 2019, 24(3), 571; https://doi.org/10.3390/molecules24030571

New Rigid Polycyclic Bis(phosphane) for Asymmetric Catalysis

1
Faculty of Chemistry, Maria Curie-Sklodowska University, 33-Gliniana St., 20-031 Lublin, Poland
2
Faculty of Pharmacy, Medical University of Lublin, 4A-Chodźki St., 20-093 Lublin, Poland
3
Department of Organic Chemistry, Cracow University of Technology, 24-Warszawska St., 31-155 Cracow, Poland
4
Pharmaceutical Research Institute, 8-Rydygiera St., 01-793 Warsaw, Poland
*
Authors to whom correspondence should be addressed.
Academic Editor: Giovanni De Feo
Received: 11 January 2019 / Revised: 30 January 2019 / Accepted: 1 February 2019 / Published: 5 February 2019
(This article belongs to the Special Issue Organophosphorus Chemistry 2018)
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Abstract

A simple, highly efficient synthesis of a series of novel chiral non-racemic rigid tetracyclic phosphorus ligands, applicable in important chemical asymmetric transformations, was performed. In a tandem cross-coupling/C-H bond activation reaction, a well-recognised and readily available ligand (R,R)-NORPHOS was used as the starting material. The palladium complexes of new ligands were obtained and characterised on the example of a crystalline dichloropalladium complex of [(1R,2R,9S,10S,11R,12R)-4-phenyltetracyclo[8.2.1.02,9.03,8]trideca-3,5,7-triene-11,12-diyl]bis(diphenylphosphane). A notably high activity and stereoselectivity of the palladium catalysts based on the new ligands were confirmed in a model asymmetric allylic substitution reaction. Herein, we discuss the geometry of the palladium complexes formed and its impact on the efficiency of the catalysts. A comparison of their geometric features with other bis(phosphane) ligand complexes found in the Cambridge Structural Database and built density functional theory (DFT) commutated models is also presented and rationalised. View Full-Text
Keywords: bis(phosphane) palladium complex; metallacycle; NORPHOS; allylic alkylation; asymmetric catalysis; chiral phosphines; C-H bond activation; polycyclic compounds; stereoselective synthesis; DFT calculations bis(phosphane) palladium complex; metallacycle; NORPHOS; allylic alkylation; asymmetric catalysis; chiral phosphines; C-H bond activation; polycyclic compounds; stereoselective synthesis; DFT calculations
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited (CC BY 4.0).

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Pietrusiewicz, K.M.; Szwaczko, K.; Mirosław, B.; Dybała, I.; Jasiński, R.; Demchuk, O.M. New Rigid Polycyclic Bis(phosphane) for Asymmetric Catalysis. Molecules 2019, 24, 571.

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