Rhodium and ruthenium complexes of methylene-bridged, <i>P</i>-stereogenic, unsymmetrical diphosphanes

Eusamio, Javier; Medina, Yaiza M.; Córdoba, Javier Carrasco; Vidal‐Ferran, Anton; Sainz, Daniel; Gutiérrez, Albert; Font-Bardı́a, Mercè; Grabulosa, Arnald

doi:10.1039/d2dt04026c

Cited by 5 publications

(8 citation statements)

References 103 publications

(237 reference statements)

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“…Interestingly, the 31 P{H} NMR spectrum of the mixture of 0.5 eq. of ( R P ) - L1 and 1eq of [Rh(cod) 2 ]BF 4 (condition-1, Scheme ) indicates the formation of a homoleptic 1:2 (M:L) complex (abbreviated as Rh-3-( R P ) - L1 as the major species with a spin system of AA’XX’, where J (AX) and J (AX’) are identical (43 Hz) Figure S5 (ESI) shows a similar distribution even in the 1:1 (M:L) reaction mixture (condtion-2, Scheme ).…”

Section: Resultsmentioning

confidence: 99%

Rh-Catalyzed Enantioselective Hydrogenation of Di- and Tri-Substituted Enamides Enabled by Easily Tunable P-Stereogenic N-Phosphinyl Phosphoramidite Ligands

Chakrabortty,

Konieczny,

Moritz

et al. 2023

ACS Catal.

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A modular mixed donor P-stereogenic narrow bite angle N-phosphinyl phosphoramidite ligand library (JoSoPhos) was synthesized. The JoSoPhos ligand library was applied to the asymmetric synthesis of the anti-Parkinson therapeutic Rasagiline in >99% ee and 79% yield via the Rh-catalyzed asymmetric hydrogenation of 1-indanone derived enamide as the key step. The Rh/ JoSoPhos catalyst also demonstrated high catalytic performance in the asymmetric hydrogenation of vinyl enamides with a broad functional group tolerance up to >99% ee. Other challenging trisubstituted vinylic olefins were also reduced with excellent enantioselection. A range of trisubstituted carbocyclic olefins bearing different functional groups were also reduced delivering products with >99% ee's. Pharmaceutically important chiral primary amines have also been prepared using the hydrogenation/ hydrolysis method in close to enantiopure form. Isotope labeling studies showed the Rh/JoSoPhos catalyzed enantioselective hydrogenation of di-and trisubstituted enamide is an isomerization-free direct asymmetric hydrogenation process.

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Section: Resultsmentioning

confidence: 99%

Rh-Catalyzed Enantioselective Hydrogenation of Di- and Tri-Substituted Enamides Enabled by Easily Tunable P-Stereogenic N-Phosphinyl Phosphoramidite Ligands

Chakrabortty,

Konieczny,

Moritz

et al. 2023

ACS Catal.

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“…Once the reaction reached completion, the resulting mixture was treated with hexane to yield a precipitate. The precipitate was then filtrated, washed multiple times with hexane to ensure purity, and dried under vacuum conditions …”

Section: Experimental Sectionmentioning

confidence: 99%

“…The precipitate was then filtrated, washed multiple times with hexane to ensure purity, and dried under vacuum conditions. 26 2.1.3. Ru(II)-Benzene Complexes.…”

Section: Pyrene-1-carboxaldehyde Tsc Ligands (L1p-l3pmentioning

confidence: 99%

Unraveling the Anticancer Efficacy and Biomolecular Properties of Ru(II)-Arene Complexes of Pyrene-Based Thiosemicarbazone Ligands: A Comprehensive In Silico/In Vitro Exploration

Vadakkedathu Palakkeezhillam,

Haribabu,

Kumar

et al. 2024

Organometallics

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We report the successful synthesis and comprehensive characterization of novel Ru(II)-arene complexes incorporating pyrene-based thiosemicarbazone (TSC) ligands. Utilizing a suite of advanced spectroscopic techniques including ultraviolet–visible (UV–visible), Fourier transform infrared (FT-IR), 1H NMR, 13C NMR, and high-resolution mass spectrometry (HRMS), the intricate structural and electronic nuances of these complexes were elucidated. X-ray crystallographic data unequivocally affirmed the ligands’ preferential coordination through the thionyl sulfur and imine nitrogen moieties with the Ru(II) ion. Rigorous density functional theory (DFT) computations reveal these complexes as exemplary electron donors, concomitantly hinting at their significant bioactive potential. Notably, molecular docking and molecular dynamic simulation studies suggest that they are potential SND1 protein inhibitors, which are essential proteins in the functioning of cancer cells. Furthermore, they have a strong affinity for binding to CT-DNA and bovine serum albumin (BSA), indicating DNA intercalation and a strong protein-binding ability. Intriguingly, the Ru-arene TSC complexes unveiled potent cytotoxic activity against an array of cancerous cell linesmost notably MDA-MB-231 (IC50 = 10.2 ± 0.02 μM), A549 (IC50 = 25.7 ± 0.07 μM), and HeLa (IC50 = 20.7 ± 0.05 μM) for RuP2P emerging as a standout agent.

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“…Figure shows C 1 -symmetric bisphosphorus ligands reported from 2001 to 2023. ,− Among these, the three-hindered quadrant bisphosphorus ligands are typical C 1 -symmetric ligands. In 2004, Hoge and co-workers reported the first distinct three-hindered quadrant bisphosphine ligand, Trichickenfootphos (TCFP) .…”

Section: A Historical Overview Of P-stereogenic Phosphorus Ligandsmentioning

confidence: 99%

P-Stereogenic Phosphorus Ligands in Asymmetric Catalysis

Imamoto

2024

Chem. Rev.

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Chiral phosphorus ligands play a crucial role in asymmetric catalysis for the efficient synthesis of useful optically active compounds. They are largely categorized into two classes: backbone chirality ligands and P-stereogenic phosphorus ligands. Most of the reported ligands belong to the former class. Privileged ones such as BINAP and DuPhos are frequently employed in a wide range of catalytic asymmetric transformations. In contrast, the latter class of P-stereogenic phosphorus ligands has remained a small family for many years mainly because of their synthetic difficulty. The late 1990s saw the emergence of novel P-stereogenic phosphorus ligands with their superior enantioinduction ability in Rh-catalyzed asymmetric hydrogenation reactions. Since then, numerous P-stereogenic phosphorus ligands have been synthesized and used in catalytic asymmetric reactions. This Review summarizes P-stereogenic phosphorus ligands reported thus far, including their stereochemical and electronic properties that afford high to excellent enantioselectivities. Examples of reactions that use this class of ligands are described together with their applications in the construction of key intermediates for the synthesis of optically active natural products and therapeutic agents. The literature covered dates back to 1968 up until December 2023, centering on studies published in the late 1990s and later years.

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Rhodium and ruthenium complexes of methylene-bridged, P-stereogenic, unsymmetrical diphosphanes

Abstract: Enantiopure P-stereogenic methylphosphane-boranes (SP)-P(BH3)PhArMe (ArMe; Ar = 1-naphthyl (NpMe), and 2-biphenylyl (BiphMe)) have been used to prepare diphosphanes of the type ArPhPCH2PR2 (R = Ph, iPr or tBu; ArR). The...

Cited by 5 publications

References 103 publications

Rh-Catalyzed Enantioselective Hydrogenation of Di- and Tri-Substituted Enamides Enabled by Easily Tunable P-Stereogenic N-Phosphinyl Phosphoramidite Ligands

Rh-Catalyzed Enantioselective Hydrogenation of Di- and Tri-Substituted Enamides Enabled by Easily Tunable P-Stereogenic N-Phosphinyl Phosphoramidite Ligands

Unraveling the Anticancer Efficacy and Biomolecular Properties of Ru(II)-Arene Complexes of Pyrene-Based Thiosemicarbazone Ligands: A Comprehensive In Silico/In Vitro Exploration

P-Stereogenic Phosphorus Ligands in Asymmetric Catalysis

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