Chiral diphosphines and diphosphinites derived from 2,2-biphosphole: Stereodynamic ligands for asymmetric catalysis

Gouygou, Maryse; Daran, Jean‐Claude; Robé, Emmanuel; Ortéga, Carmen

doi:10.1016/j.crci.2010.03.003

Cited by 8 publications

(9 citation statements)

References 24 publications

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“…5 48 %), with almost equal amounts of 3 SSS (ca. Interconversion of stereoisomers has been observed for the heterocycles 3 RSS , 3 RSR and 4 RSR and was studied, with the representative compound 3 RSS in deuterated benzene, by 31 P NMR spectroscopy (Scheme 4).…”

Section: Racemisation Kinetics and Configurative Stabilitymentioning

confidence: 99%

“…5 Bis{(3R,6S)-3,6-diphenyl-1-[(1R)-1-phenylpropyl]-1-aza-3,6-diphos-phacycloheptane}platinum(II) Dichloride (9): A solution of dichloro(1,5-cyclooctadiene)platinum(II) (0.07 g, 0.2 mmol) in CH 2 Cl 2 (10 mL) was added dropwise to a solution of 5 (0.27 g, 0.7 mmol, containing 55 % 5 RSR , 30 % 5 RRR and 15 % 5 SSR ) in CH 2 Cl 2 (10 mL). The reaction mixture was stirred at ambient temperature for 30 min.…”

Section: Cis-dichloro-(3r6s)-1-[(1r)-1-(4ј-methoxyphenyl)ethyl]-36-mentioning

confidence: 99%

“…k -1 = k 1 /K eq1 , and k -2 = k 2 /K eq2 (5) The equilibrium concentrations c aeq , c beq , c ceq were measured experimentally. Calculations of the kinetic parameters were performed for the isomerization reactions performed at 295.5 and 343 K.…”

Section: Cis-dichloro-(3r6s)-1-[(1r)-1-(4ј-methoxyphenyl)ethyl]-36-mentioning

confidence: 99%

“…[1][2][3][4] Chiral chelating bisphosphanes are of special interest due to their high effectiveness in many asymmetric catalytic reactions. However, transition metal complexes of bisphosphanes bearing P-stereogenic or P-and C-stereogenic centers have proved to be excellent catalysts for asymmetric allylic substitution, [5] asymmetric hydrogenation, [5,6,7] asymmetric hydroformylation, [5,8] and asymmetric hydrosilylation [7,9] reactions, and display high enantioselectivity. The fast and selective formation of the cationic complex (9) of the meso isomer 5 RSR allowed for the separation of the 5 RRR and 5 SSR isomers of the bisphosphane 5.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis and Stereoselective Interconversion of Chiral 1‐Aza‐3,6‐diphosphacycloheptanes

et al. 2012

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Cyclic seven-membered bisphosphanes, namely 1-aza-3,6diphosphacycloheptanes 3-5 (3: 3,6-diphenyl-1-(1-phenylethyl)-1-aza-3,6-diphosphacycloheptane; 4: 1-[(1R)-1-(4Јmethoxyphenyl)ethyl]-3,6-diphenyl-1-aza-3,6-diphosphacycloheptane; 5: 3,6-diphenyl-1-[(1R)-1-phenylpropyl]-1-aza-3,6-diphosphacycloheptane), with chiral exocyclic substituents at the nitrogen positions have been synthesized, with the prevailing formation of meso stereoisomers (P R P S ) as kinetically controlled products, by stereoselective condensation of 1,2-bis(phenylphosphanyl)ethane, formaldehyde and primary optically pure amines, namely (S)-(-)-1-phenylethylamine, (R)-(+)-1-phenylethylamine, (R)-(+)-1-phenylpropylamine, (R)-(+)-1-(4Ј-methoxyphenyl)ethylamine. The meso stereoisomers of bisphosphanes 3 RSS , 3-5 RSR readily form neutral and cationic P,P-chelate complexes 6-9 with platinum(II) (6:

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Section: Racemisation Kinetics and Configurative Stabilitymentioning

confidence: 99%

Section: Cis-dichloro-(3r6s)-1-[(1r)-1-(4ј-methoxyphenyl)ethyl]-36-mentioning

confidence: 99%

Section: Cis-dichloro-(3r6s)-1-[(1r)-1-(4ј-methoxyphenyl)ethyl]-36-mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Synthesis and Stereoselective Interconversion of Chiral 1‐Aza‐3,6‐diphosphacycloheptanes

et al. 2012

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“…Initially successful phosphines have given way to less electron rich P‐donor ligands (i.e. phosphites,, phosphonites, phosphinites, and phosphoramidites) due to increased activities and higher resistances towards oxidation. To date, the most active and iso ‐selective catalysts for styrene hydroformylation are Rh I complexes of chelating phosphite or phospholane ligands, or hybrids thereof , .…”

Section: Introductionmentioning

confidence: 99%

Comparative Study of Novel Phosphordiamidite and Phosphite Ligands Used in Alkene Hydroformylation; Synthesis, Characterization, Metalation, and Catalytic Evaluation

et al. 2018

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Three novel ligands have been prepared by the reactions of 1,1′-(chlorophosphinediyl)bis(1H-pyrrole) with either 2pyridinemethanol or 2,6-pyridinedimethanol or the reaction of 1,1′-biphenyl-2,2′-diyl phosphorochloridite with 2-pyridinemethanol. Measurement of | 1 J P-Se | values demonstrate that the phosphite donor is less basic than the phosphoramidite donors. Coordination preferences of the ligands in octahedral cis-tetracarbonylmolybdenum(0) and square planar cis-dichloropalladium(II) complexes have been evaluated using multinuclear NMR and X-ray crystallography. Rhodium(I) complexes of the Scheme 2. Synthesis of chelating molybdenum complexes 1-3.Scheme 3. Synthesis of palladium chelating complexes 4, 5 and 6.

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Enantioselective Hydroformylation

2021

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Hydroformylation is powerful catalytic reaction capable of converting alkenes directly into aldehydes by addition of a formyl group and hydrogen across the double bond. Installation of the formyl group at an internal carbon establishes a chiral center, and a variety of chiral ligands may be employed to direct the enantioselectivity of the reaction. The alkene substrates are easily accessed, and the resultant aldehydes are common precursors for diverse synthetic manipulations. This chapter covers enantioselective hydroformylation from its inception, presents the most common metal precursors and ligands, and includes all examples that produce aldehydes with yields above 20% and enantioselectivity above 60:40 er. The initial discussion focuses on the mechanism and stereochemistry, and on the regio‐ and enantioselectivity‐determining steps in particular, as these are crucial for overall yield. The “Scope and Limitations” section is divided by substrate type and offers examples of exceptional catalytic systems that have been reported for each. The application of enantioselective hydroformylation to synthetic procedures is discussed by highlighting some reported examples, comparing it to other protocols that also afford chiral aldehydes, and exploring the standard experimental conditions. The intention of this review is to demonstrate the power and scope of enantioselective hydroformylation to researchers, and to provide a suitable starting point for those interested in its application to their own synthetic strategies.

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Chiral diphosphines and diphosphinites derived from 2,2-biphosphole: Stereodynamic ligands for asymmetric catalysis

Cited by 8 publications

References 24 publications

Synthesis and Stereoselective Interconversion of Chiral 1‐Aza‐3,6‐diphosphacycloheptanes

Synthesis and Stereoselective Interconversion of Chiral 1‐Aza‐3,6‐diphosphacycloheptanes

Comparative Study of Novel Phosphordiamidite and Phosphite Ligands Used in Alkene Hydroformylation; Synthesis, Characterization, Metalation, and Catalytic Evaluation

Enantioselective Hydroformylation

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