Organic Chemistry: Current Research
Open Access

Intramolecular nucleophilic substitution of haloalkylphosphine derivatives

10^th European Organic Chemistry Congress

March 21-22, 2019 | Rome, Italy

Pawel Woznicki, Ewelina Buczak and Marek Stankevic

Maria Curie-Sklodowska University, Poland

Scientific Tracks Abstracts: Organic Chem Curr Res

Abstract :

Organophosphorus compounds are one of the main classes of ligands used in transition metal-catalyzed reactions such as cross-coupling, catalytic hydrogenation and olefin metathesis. Among them cycloalkyl and P-heterocyclic phosphines constitute an important subgroup with good σ-donating ability and medium to high steric hindrance, these properties render them suitable for palladium- and nickel-catalyzed cross-coupling of less reactive or deactivated substrates such as aryl chlorides with electron-donating substituents, aryl sulfonates, aryl carboxylates, and aryl ethers. We have developed a new method of the synthesis of cyclic di- and monoarylphosphine derivatives through haloalkylation of simple secondary or tertiary phosphine-boranes and sulfides followed by α-metallation and intramolecular nucleophilic substitution of halide at the terminal carbon atom. Depending on the properties of the phosphorus group and the length of the haloalkyl substituent monoarylphosphine derivatives led to the formation of P-cycloalkyl or P-heterocyclic products. The use of chiral butyllithium-sparteine base allowed the formation of chiral non-racemic cycloalkylphosphine analogues which were used to synthesize diphosphine ligand precursors via iron-mediated homocoupling. Financial support from National Science Centre (grant No 2012/07/E/ ST5/00544) is kindly acknowledged.

Recent Publications

1. R. J. Lundgren, M. Stradiotto (2012), Addressing Challenges in Palladiumâ�?Catalyzed Crossâ�?Coupling Reactions Through Ligand Design, Chem. Eur. J., 18:9758–9769.

2. P. G. Gildner, T. J. Colacot (2015), Reactions of the 21st Century: Two Decades of Innovative Catalyst Design for Palladium-Catalyzed Cross-Couplings, Organometallics, 34:5497–5508.

3. C. Samoj�?�?owicz, M. Bieniek, K. Grela (2009), Ruthenium-Based Olefin Metathesis Catalysts Bearing N-Heterocyclic Carbene Ligands, Chem. Rev., 109:3708–3742.

4. T. Ishiyama, K. Ishida, N. Miyaura (2001), Synthesis of pinacol arylboronates via cross-coupling reaction of bis(pinacolato)diboron with chloroarenes catalyzed by palladium(0)–tricyclohexylphosphine complexes, Tetrahedron, 57:9813–9816.

5. D. Zim, V. R. Lando, J. Dupont, A. L. Monteiro (2001), NiCl2(PCy3)2: A Simple and Efficient Catalyst Precursor for the Suzuki Cross-Coupling of Aryl Tosylates and Arylboronic Acids, Org. Lett., 3:3049–3051.

6. J. Yang, J. Xiao, T. Chen, L.-B. Han (2016), Nickel-Catalyzed Phosphorylation of Phenol Derivatives via C–O/ P–H Cross-Coupling, J. Org. Chem., 81:3911–3916.

Biography :

Pawe�?�? Wo�?ºnicki was born in 1990. In 2017 he obtained his bachelor's degree in chemistry from Maria Curie-Sk�?�?odowska University in Lublin where he has been conducting research under the supervision of Professor Marek Stankevi�?. In 2017 he received Scholarship of Minister of Science and Higher Education. In 2018 he was awarded "Diamond Grant", an annual grant awarded by the Polish Minister of Science and Higher Education to students holding a bachelor's or engineer's degree. Currently he continues his research as a doctoral student. His academic interests include synthesis of organophosphorus compounds, stereoselective synthesis and transition metal-catalyzed transformations.