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Synlett 2022; 33(18): 1841-1846
DOI: 10.1055/s-0042-1752342
DOI: 10.1055/s-0042-1752342
cluster
Development and Applications of Novel Ligands/Catalysts and Mechanistic Studies on
Catalysis
The Synthesis of Novel P,N-Ferrocenylpyrrolidine-Containing Ligands and Their Application in Pd-Catalyzed Allylic Alkylation – A Synthetic and Mechanistic Investigation
The acquisition of mass spectra was supported by a Science Foundation Ireland Infrastructure Award (18/RI/5702). We thank the University College Dublin (UCD) School of Chemistry for a Research Demonstratorship award to T.B.B. We also acknowledge the facilities of the Centre for Synthesis and Chemical Biology (CSCB), which was funded through the Higher Education Authority’s Programme for Research in Third-Level Institutions (PRTLI).
Abstract
The synthesis of a series of planar chiral P,N-ferrocenylpyrrolidine-containing ligands, with varying substituents at the phosphorus donor atom, is described. The phosphorus donor atom was introduced via a diastereoselective ortho-directed metalation of N-methylpyrrolidinyl ferrocene followed by a quench with various chlorophosphines. These P,N systems are very active in Pd-catalyzed allylic alkylation of 1,3-diphenylpropenyl acetate with dimethylmalonate (conversions of up to 100%) and demonstrated good levels of enantioselectivity (up to 85% ees). Good selectivity for the (R)-enantiomer was observed and mechanistic studies, involving X-ray crystallography and NMR spectroscopic experiments, were employed to help rationalize the observed stereochemical outcome of the reaction.
Key words
ferrocene - chiral ligand - pyrrolidine - asymmetric catalysis - Pd-catalyzed allylic alkylationSupporting Information
- Supporting information for this article is available online at
https://doi.org/10.1055/s-0042-1752342.
- Supporting Information
- CIF File
Publikationsverlauf
Eingereicht: 23. August 2022
Angenommen nach Revision: 06. September 2022
Artikel online veröffentlicht:
12. Oktober 2022
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- 39 Preparation of 2-[(2R)-N-Methylpyrrolidin-2′yl]-(1R)-ferrocenyldi(aryl/alkyl)-phosphines 8a–c To a solution of (R)-1-ferrocenyl-2-methylpyrrolidine (7, 0.63 g, 2.12 mmol) in dry diethyl ether (7 mL) at –78 °C, sec-butyllithium (1.97 mL, 1.4 M, 2.76 mmol) was added dropwise. The orange suspension was stirred for 3 h at this temperature and at 0 °C for 90 min to ensure complete lithiation. The relevant chlorophosphine (2.76 mmol) was added as a solution in diethyl ether (3 mL) at 0 °C, and the reaction was stirred at room temperature for a further hour. The reaction was quenched with 10 % ammonium chloride (5 mL) and extracted with diethyl ether (3 × 8 mL). The combined organic layers were washed with water (10 mL), brine (10 mL), dried (Na2SO4), and concentrated to give the crude product as an orange oil. The crude product contained a mixture of diastereomers (80–85% de), which were separated by column chromatography. Analytical Data of Compound (R,R p)-8a Isolated as an orange sticky solid in 51% yield; Rf = 0.64 (Al, 5:1 pentane/ethyl acetate); [α]D +184.0 (c = 0.5, CHCl3). IR (KBr disc): νmax = 3020, 2926, 2400, 1216 cm–1. 1H NMR (600 MHz, CDCl3): δ = 1.15–1.50 (m, 9 H, Cy), 1.55–1.75 (m, 8 H, Cy, H4′b), 1.85–1.90 (m, 3 H, Cy, H4′a), 1.95–2.10 (m, 3 H, Cy), 2.18–2.25 (m, 2 H, H3′b, H5′b), 2.27 (s, 3 H, N–Me), 2.32–2.38 (m, 1 H, Cy), 2.40–2.48 (m, 1 H, H3′a), 2.97 (app t, J = 8.0 Hz, 1 H, H2′), 3.07 (app t, J = 8.0 Hz, 1 H, H5′a), 4.10 (br s, 1 H, CpH5), 4.13 (s, 5 H, unsub. Cp), 4.21 (br s, 1 H, CpH3), 4.23 (app t, J = 2.1 Hz, 1 H, CpH4). 13C NMR (151 MHz, CDCl3): δ = 23.0 (d, 5 J P,C = 1.0 Hz, C4′), 26.5 (d, 4 J P,C = 1.0 Hz, Cy), 26.6 (d, 4 J P,C = 1.0 Hz, Cy), 27.3 (d, 3 J P,C = 7.5 Hz, Cy), 27.6 (d, 3 J P,C = 7.4 Hz, Cy), 27.7 (d, 2 J P,C = 13.2 Hz, Cy), 28.2 (d, 2 J P,C = 12.3 Hz, Cy), 29.1 (d, 3 J P,C = 7.5 Hz, Cy), 30.1 (d, 3 J P.C = 8.8 Hz, Cy), 32.1 (d, 2 J P,C = 16.4 Hz, Cy), 32.7 (d, 2 J P,C = 20.2 Hz, Cy), 33.6 (d, 4 J P,C = 12.1 Hz, C3’), 35.0 (d, 1 J P,C = 12.5 Hz, Cy), 36.3 (d, 1 J P,C = 13.0 Hz, Cy), 40.9 (N–Me), 58.1 (C5′), 66.0 (d, 3 J P,C = 1.7 Hz, C2′), 67.5 (CpC4), 69.5 (Cp), 70.8 (d, 3 J P,C = 3.0 Hz, CpC3), 71.0 (d, 2 J P,C = 2.5 Hz, CpC5), 77.7 (d, 1 J P,C = 22.7 Hz, CpC1), 94.2 (d, 2 J P,C = 16.7 Hz, CpC2). 31P NMR (243 MHz, CDCl3): δ = –11.0. Anal. Calcd for C27H40FeNP: C, 69.67; H, 8.66; N, 3.01. Found: C, 70.07; H, 8.75; N, 2.74. ESI-HRMS: m/z calcd for C27H40FeNP [M + H]: 466.2326; found: 466.2343.