Chiral Tridentate-Based Ligands

Bandyopadhyay, Uchchhal; Sundararaju, Basker; Poli, Rinaldo; Manoury, Éric

doi:10.1201/9780367855734-5

Cited by 1 publication

(2 citation statements)

References 136 publications

(143 reference statements)

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“…The great significance of this achievement is clearly indicated by the fact that many chiral catalysts of this type have now been prepared, commercialized, and successfully applied in asymmetric hydrogenation of a number of ketonic substrates, 9 even in an industrial scale 10 . Despite the success of [RuCl 2 (diphosphine)(diamine)] catalysts utilizing two (chiral) bidentate ligands, there is an ongoing interest in the development of new types of transition metal catalysts containing chiral tridentate ligands 11 . Compared to bidentate ligands, tridentate systems are more suitable for structural variations and stereoelectronic fine‐tuning, provide more coordination modes (i.e., fac ‐/ mer ‐isomerism), and may increase the thermodynamic stability of the transition metal complexes.…”

Section: Introductionmentioning

confidence: 99%

“…10 Despite the success of [RuCl 2 (diphosphine)(diamine)] catalysts utilizing two (chiral) bidentate ligands, there is an ongoing interest in the development of new types of transition metal catalysts containing chiral tridentate ligands. 11 Compared to bidentate ligands, tridentate systems are more suitable for structural variations and stereoelectronic fine-tuning, provide more coordination modes (i.e., fac-/mer-isomerism), and may increase the thermodynamic stability of the transition metal complexes. These advantageous features clearly stimulated the development of new chiral tridentate ligands and their utilization in transition metal-catalyzed asymmetric C=O hydrogenation reactions.…”

Section: Introductionmentioning

confidence: 99%

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Ruthenium complexes of new chiral phosphine‐amine‐ether ligands (Ru‐PNO) for asymmetric hydrogenation – the role of backbone chirality in pincer ligand design

Császár,

Pőrgye,

Tóth‐Farsang

et al. 2024

Applied Organom Chemis

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New chiral phosphine‐amine‐ether (PNO) ligands of the general formula Ph2PCH(R1)(CH2)nCH(R1)N(R2)CH(R3)CH2OMe, where R1, R2, and R3 = H or Me, n = 0 or 1, and their ruthenium complexes of the type [RuCl2(PPh3)(PNO)] have been synthesized. The coordination compounds were characterized by 1D and 2D NMR spectroscopy, modeled by DFT calculations, and in one case analyzed by X‐ray crystallography. The combined spectroscopic and theoretical investigations revealed that the relative configuration of the stereogenic elements in the P–N and N–O backbone represents a crucial factor in determining the conformation of the pincer‐type chelates and may also affect the configuration of the coordinated stereogenic nitrogen in the NH subunit, an essential element of stereochemical communication in outer sphere bifunctional catalysis. The new complexes were applied in the asymmetric hydrogenation of fused ring bicyclic ketones (i.e., 1‐tetralone and 4‐chromanone derivatives), a challenging substrate class, where enantioselectivities up to 97% could be obtained. Based on the spectroscopic and theoretical studies and catalytic experiments, structural features affecting the stereochemistry of the coordination could be identified and a qualitative enantioinduction model has been proposed.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%