Evolution in heterodonor P-N, P-S and P-O chiral ligands for preparing efficient catalysts for asymmetric catalysis. From design to applications

Margalef, Jèssica; Biosca, Maria; Sánchez, Pol de la Cruz; Faiges, Jorge; Pàmies, Òscar; Diéguez, Montserrat

doi:10.1016/j.ccr.2021.214120

Cited by 61 publications

(37 citation statements)

References 638 publications

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“…This exceptional activity results from both electronic and stereo effects: on one hand, the π-acidic character of the phosphite weakens the metal-CO bond, thereby allowing a faster CO dissociation; on the other hand, the ligand’s large cone angle allows the coordination of only one phosphite to the metal centre, even when used in large excess, which results in a low global steric hindrance around the metal centre [ 17 , 18 ]. Moreover, the design and synthesis of chiral phosphite ligands also play a key role in the development of asymmetric catalysis [ 19 , 20 , 21 , 22 ]. Among them, monophosphite ligands based on the binaphthyl backbone [ 23 ] have earned a prominent status due to their synthetic availability and efficient applications in a large number of enantioselective catalytic reactions, namely in hydrogenation [ 24 , 25 , 26 , 27 , 28 ], hydrovinylation [ 29 , 30 ] and allylic substitutions [ 28 , 31 , 32 , 33 , 34 ].…”

Section: Introductionmentioning

confidence: 99%

Stereoisomeric Tris-BINOL-Menthol Bulky Monophosphites: Synthesis, Characterisation and Application in Rhodium-Catalysed Hydroformylation

et al. 2022

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Four stereoisomeric monoether derivatives, based on axially chiral (R)- or (S)-BINOL bearing a chiral (+)- or (−)-neomenthyloxy group were synthesised and fully characterised by NMR spectroscopy and X-ray crystallography. The respective tris-monophosphites were thereof prepared and fully characterised. The coordination ability of the new bulky phosphites with Rh(CO)2(acac), was attested by 31P NMR, which presented a doublet in the range of δ = 120 ppm, with a 1J(103Rh-31P) coupling constant of 290 Hz. The new tris-binaphthyl phosphite ligands were further characterised by DFT computational methods, which allowed us to calculate an electronic (CEP) parameter of 2083.2 cm−1 and an extremely large cone angle of 345°, decreasing to 265° upon coordination with a metal atom. Furthermore, the monophosphites were applied as ligands in rhodium-catalysed hydroformylation of styrene, leading to complete conversions in 4 h, 100% chemoselectivity for aldehydes and up to 98% iso-regioselectivity. The Rh(I)/phosphite catalytic system was also highly active and selective in the hydroformylation of disubstituted olefins, including (E)-prop-1-en-1-ylbenzene and prop-1-en-2-ylbenzene.

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Section: Introductionmentioning

confidence: 99%

Stereoisomeric Tris-BINOL-Menthol Bulky Monophosphites: Synthesis, Characterisation and Application in Rhodium-Catalysed Hydroformylation

et al. 2022

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“…Among phosphorus ligands, chiral phosphite-type compounds with three P–O and/or P–N bonds are of particular interest. − ,,,,,, The use of mixed-donor bidentate ligands can be most advantageous. Specifically, nonsymmetrical thioether-containing phosphite ligands with two electronically and sterically different P and S donor centers are very interesting . The known P , S -bidentate phosphites L A and phosphoramidites L B (Figure ) have been successfully used in a wide range of enantioselective metal-catalyzed reactions. , …”

Section: Introductionmentioning

confidence: 99%

Formation of Allylpalladium Complexes and Asymmetric Allylation Involving Modular Bridging Diamidophosphite-Sulfides Based on 1,4-Thioether Alcohols

Chuchelkin

Gavrilov

et al. 2021

Organometallics

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A large family of P,S-bidentate diamidophosphite ligands were readily synthesized from accessible hydroxyl-thioether compounds. One type of Pd(II) cationic allylic complex with these diamidophosphites fulfilling a P-monodentate function, and three types, where the ligands act as P,S-bridging ligands (coordination polymer and head-to-head and head-to-tail dimers), were obtained. In addition, neutral Pd(II) halide complexes were generated in situ as common intermediates for both groups of cationic dimers. The structures of the ligands and complexes were elucidated by means of 2D-NMR and were confirmed by powder X-ray diffraction, as well as by DFT calculations. Asymmetric inducers of this type exhibited up to 94% ee in the Pd-mediated allylic substitution of (E)-1,3-diphenylallyl acetate with various C- and N-nucleophiles. Ee values of up to 80% were obtained in the Pd-catalyzed allylic alkylation of cinnamyl acetate with β-ketoesters. In addition, up to 61% ee was achieved in the asymmetric amination of 2-(diethoxyphosphoryl)-1-phenylallyl acetate with aniline. The effects of the diamidophosphite and thioether moieties on the catalytic activity and enantioselectivity were investigated.

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“…This catalyst was carried forward and tested with P,N-bidentate ligands L1 and L2 which are known to impart regio-and enantioselectivity in allylic substitution reactions through the difference in the P versus N donor atoms on the ligand (Figure 2 entries 5 & 6). 57,60 A modest, yet promising increase in regioselectivity was observed using L1 (64:36) but the yield decreased to 47%. Using L2, the yield plummeted to 4%.…”

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confidence: 99%

“…[54][55][56] Inspired by reports in the allylic substitution literature, we hypothesized that selectivity could be controlled by a metal catalyst with an unsymmetrical ligand environment such as those induced by phosphinooxazoline (PHOX) ligands. [57][58][59][60][61] If a C1 symmetric ligand environment could be created, then selectivity could potentially be induced in aryne reactions as well. Herein we report a Pd-catalyzed annulation reaction with up to 91:9 r.r.…”

mentioning

confidence: 99%

Superseding Substrate Control with Catalyst Control to Improve Regioselectivity in Aryne Annulations

Denman

Plasek

Roberts

2022

Preprint

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The utility of reactions using unsymmetrically substituted aryne intermediates is negatively impacted by issues with regiose-lectivity. There have been numerous reports about how to enhance or reverse this regioselectivity in free aryne reactions by altering the electronics of the substrate. To the best of our knowledge, no such studies exist for systems with metal-bound aryne intermediates, which often suffer from worse regioselectivities. Herein we report a means of achieving regioselectivity in a metal catalyzed aryne difunctionalization via catalyst control. Through the use of an unsymmetrical ligand environment, selectivity can be induced (up to 91:9 r.r.). We also report the reversal of regioselectivity between ligand environments. These investigations demonstrate that catalyst control can supersede substrate control in metal-catalyzed aryne reactions.

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Evolution in heterodonor P-N, P-S and P-O chiral ligands for preparing efficient catalysts for asymmetric catalysis. From design to applications

Cited by 61 publications

References 638 publications

Stereoisomeric Tris-BINOL-Menthol Bulky Monophosphites: Synthesis, Characterisation and Application in Rhodium-Catalysed Hydroformylation

Stereoisomeric Tris-BINOL-Menthol Bulky Monophosphites: Synthesis, Characterisation and Application in Rhodium-Catalysed Hydroformylation

Formation of Allylpalladium Complexes and Asymmetric Allylation Involving Modular Bridging Diamidophosphite-Sulfides Based on 1,4-Thioether Alcohols

Superseding Substrate Control with Catalyst Control to Improve Regioselectivity in Aryne Annulations

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