Efficient, Rhodium‐Catalyzed Hydrogenation of α‐Dehydroamino Acid Esters with Chiral Monodentate Aminophosphanes Bearing Two Binaphthyl Groups

Eberhardt, Luc; Armspach, Dominique; Matt, Dominique; Toupet, Loı̈c; Oswald, Benoít

doi:10.1002/ejoc.200700533

Cited by 15 publications

(4 citation statements)

References 42 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…37 For the other two methods, the yields do not surpass 50%. Most phosphoramidites are stable towards oxygen, but some of them were reported 38,39 to easily undergo P-N cleavage in the presence of protic solvents (note that MonoPhos is stable in MeOH 31 and towards hydrolysis). 33 In all these ligands, the phosphorus atom is part of a heterocyclic ring, a feature which certainly contributes to the good stability towards air.…”

Section: Preparation Of Binol-derived Phosphoramiditesmentioning

confidence: 99%

“…Eberhardt et al recently synthesized the phosphoramidites 108, all containing a chiral dinaphtho-azepinyl moiety, and found that rhodium complexes of the latter led to high hydrogenations rates with olefins 1, 5 and 6. 39 The highest enantioselectivities, up to 99% (! ), were achieved for those stereomers of 108 having two chiral binaphthyl groups with opposite configurations.…”

Section: Phosphoramidites With Amino Groups Containing At Least One S...mentioning

confidence: 99%

See 1 more Smart Citation

BINOL-derived phosphoramidites in asymmetric hydrogenation: can the presence of a functionality in the amino group influence the catalytic outcome?

et al. 2008

Self Cite

View full text Add to dashboard Cite

In discovering the remarkable catalytic properties of BINOL-derived phosphoramidites (binoP-NR(2)), Dutch researchers recently achieved a long-awaited breakthrough in asymmetric catalysis. For the first time, easily accessible monodentate chiral P(III) ligands turned out to provide high enantioselectivities when used in rhodium-catalysed olefin hydrogenation. The simplest ligand representative of this family is MonoPhos, which can be made straightforwardly from BINOL and hexamethylphosphorous triamide. Since the first publication dealing with such catalysts (J. Am. Chem. Soc., 2000), a variety of binoP-NRR' ligands have been reported in which the amino group bears a functional substituent or a stereogenic centre. This critical review examines the impact of the presence of such a functionality in the amino group on catalytic olefin hydrogenation reactions.

show abstract

Section: Preparation Of Binol-derived Phosphoramiditesmentioning

confidence: 99%

Section: Phosphoramidites With Amino Groups Containing At Least One S...mentioning

confidence: 99%

BINOL-derived phosphoramidites in asymmetric hydrogenation: can the presence of a functionality in the amino group influence the catalytic outcome?

et al. 2008

Self Cite

View full text Add to dashboard Cite

show abstract

“…This class of monodentate ligand has been highly successful in asymmetric catalysis, including gold catalysis . Thus, secondary amine 1 was treated with both enantiomeric binaphthol‐derived phosphochloridites 2 and 3 in toluene in the presence of N , N ‐diisopropylethylamine (Hünig's base) to give respectively phosphoramidites 4 and 5 . While ( S )‐binaphthyl ligand 4 could be isolated in excellent yield (98 %), its R counterpart proved to be much less stable and therefore was used without chromatographic purification (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

A Comparative Study of Confining Ligands Derived from Methylated Cyclodextrins in Gold‐Catalyzed Cycloisomerization of 1,6‐Enynes

et al. 2019

Self Cite

View full text Add to dashboard Cite

Gold(I) complexes containing monodentate PIII‐ligands built upon methylated α‐cyclodextrins have been synthesized and assessed in the cycloisomerization of 1,6‐enynes, two of the reactions studied involving prochiral substrates. Their performance was compared with that of previously reported mononuclear and dinuclear α‐ and β‐cyclodextrin‐based AuI complexes. Enantiodiscrimination was found to be strongly dependent on the ability of the ligand to position metal‐coordinated substrates inside the cyclodextrin core.

show abstract

“…The observed J(PPt) coupling constant, 5609 Hz, is typical for a platinum complex with two cis-disposed phosphoramidites. [10][11][12] The X-ray structure of (S,S)-10 (Fig. 1) reveals a ligand bite angle of 84.4 • and an almost planar PtP 2 Cl 2 unit (maximum deviation from this plane: 0.093 A ˚).…”

Section: Resultsmentioning

confidence: 99%

Efficient asymmetric hydrogenation of olefins with hydrazine-derived diphosphoramidites

et al. 2007

Self Cite

View full text Add to dashboard Cite

Enantiopure, BINOL-derived diphosphoramidites built upon an achiral hydrazine spacer are efficient ligands for the hydrogenation of 2-(acetylamino)-3-(aryl)-propenoic methyl esters. The activity and enantioselectivity of the hydrazine derivatives were shown to be markedly influenced by the nature of the two NR substituents, symmetrical but bulky R groups leading to the best results. A diphosphosphoramidite obtained from (t)BuHNNH(t)Bu resulted in ee's as high as 95%. The present results contradict previous reports on "short" diphosphoramidites.

show abstract

Efficient, Rhodium‐Catalyzed Hydrogenation of α‐Dehydroamino Acid Esters with Chiral Monodentate Aminophosphanes Bearing Two Binaphthyl Groups

Cited by 15 publications

References 42 publications

BINOL-derived phosphoramidites in asymmetric hydrogenation: can the presence of a functionality in the amino group influence the catalytic outcome?

BINOL-derived phosphoramidites in asymmetric hydrogenation: can the presence of a functionality in the amino group influence the catalytic outcome?

A Comparative Study of Confining Ligands Derived from Methylated Cyclodextrins in Gold‐Catalyzed Cycloisomerization of 1,6‐Enynes

Efficient asymmetric hydrogenation of olefins with hydrazine-derived diphosphoramidites

Contact Info

Product

Resources

About