Enantiopure 1-r-H-2-c,5-t-diphenylphospholane as ligand in Rh-catalyzed asymmetric hydrogenation

Galland, Aurore; Dobrotă, Cristian; Toffano, Martial; Fiaud, Jean‐Claude

doi:10.1016/j.tetasy.2006.08.020

Cited by 29 publications

(22 citation statements)

References 9 publications

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“…No other signals are detected. The presence of complex A is based on previous work 11b,11c,14. Furthermore, we observed no signal in the range from 0 to –30 ppm in the 1 H NMR spectrum, corresponding to the [Rh]–H bond 4a,7c,15.…”

Section: Resultsmentioning

confidence: 99%

Regioselective Metal‐Catalyzed Hydrophosphinylation of Alkynes: Synthesis of Enantiopure α‐ or β‐Substituted Vinylphosphane Oxides

Duraud¹,

Toffano²,

Fiaud³

2009

Eur J Org Chem

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Palladium was found to catalyze regioselective Markovnikov addition of chiral enantiopure 1r-oxo-2c,5t-diphenylphospholane (1) to terminal alkynes, whereas rhodium catalysis offers selectively the (E)-anti-Markovnikov adduct. ThisSupporting Information (see footnote on the first page of this article): Experimental procedures, characterization data and copies of the 1 H, 13 C and 31 P NMR spectra.www.eurjoc.org

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Section: Resultsmentioning

confidence: 99%

Regioselective Metal‐Catalyzed Hydrophosphinylation of Alkynes: Synthesis of Enantiopure α‐ or β‐Substituted Vinylphosphane Oxides

Duraud¹,

Toffano²,

Fiaud³

2009

Eur J Org Chem

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“…In this context, we thought enantiopure trans ‐2,5‐diphenylphospholane ( 1 ) could be alkylated with simpleelectrophiles. This compound is obtained in two stepsfrom 1‐oxo‐1‐hydroxy‐2,5‐diphenylphospholanic acid (Scheme ) 14…”

Section: Resultsmentioning

confidence: 99%

“…tert ‐Butyl chloride, benhydryl chloride, silver trifluoromethanesulfonate were purchased from Acros, and methyl triflate was purchased from Fluka. The synthesis and experimental data of (2 S ,5 S )‐diphenylphospholane ( 1 ) were reported in our previous papers 3,14…”

Section: Methodsmentioning

confidence: 99%

Synthesis of Enantiopure 1‐r‐Alkyl‐2‐c,5‐t‐Diphenylphospholanes and Phospholanium Salts through Direct Alkylation of Phospholane

et al. 2008

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“…The aryl-substituted phosphines are better chiral ligands than the alkyl-substituted ones, with the monophosphine 36a being the most efficient ligand. Furthermore, secondary monophosphine ligand, (2S,5S)-2,5-diphenylphospholane, was also used in the rhodium-catalyzed asymmetric hydrogenation of b-substituted enamide for the synthesis of chiral N-acetyl amines, albeit with low enantioselectivity (<28% ee) [46].…”

Section: Other Chiral Monodentate Phosphorus Ligandsmentioning

confidence: 99%

Enantioselective Hydrogenation of Enamines with Monodentate Phosphorus Ligands

Zhou

Xie

2010

Chiral Amine Synthesis

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Chiral amines are widely used as chiral ligands, auxiliaries, resolving agents, and important intermediates in synthetic chemistry. Asymmetric hydrogenation of enamines such as enamides is an atom economic and straightforward protocol for the preparation of chiral amines. In 1972, Kagan reported the first example of asymmetric hydrogenation of enamides with chiral Rh-DIOP complex as a catalyst [1]. This opened a new window for the asymmetric synthesis of chiral N-acyl amines although the enantioselectivity of the reaction was not more than 78% ee (Scheme 8.1). When Noyori et al. introduced chiral Ru-BINAP, it significantly increased the level of enantioselectivity to 99.5% ee in the asymmetric hydrogenation of N-acyl-1-alkylidenetetrahydroisoquinolines [2]. However, this ruthenium-catalyzed asymmetric hydrogenation is very sensitive to the stereochemistry of the enamide, with only the (Z)-isomer of the enamide being hydrogenated while the (E)-isomer was recovered intact (Scheme 8.2). Another breakthrough in this field came in 1996 when Burk et al. showed that chiral rhodium complexes bearing a diphosphine ligand Me-DuPHOS or Me-BPE could hydrogenate a-arylenamides to yield a wide variety of valuable a-1-arylethylamine derivatives with high enantioselectivities (up to 98.5% ee) (Scheme 8.3) [3]. The merit of this hydrogenation is that both (E)-and (Z)-isomers of b-substituted enamides can be hydrogenated, thus enlarging the substrate scope of the reaction. Subsequently, many efficient diphosphines, such as BICP (bis(diphenylphosphino)dicyclopentane) [4], PennPhosP, NHAc NHAc 1 bar H 2 [RhCl(COD) 2 ] 2 /(S,S)-DIOP EtOH-C 6 H 6 (2 :1), rt 95% yield, 78% ee PPh 2 PPh 2 O O (S,S)-DIOP Scheme 8.1 Rh-DIOP catalyzed asymmetric hydrogenation of enamides.

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Enantiopure 1-r-H-2-c,5-t-diphenylphospholane as ligand in Rh-catalyzed asymmetric hydrogenation

Cited by 29 publications

References 9 publications

Regioselective Metal‐Catalyzed Hydrophosphinylation of Alkynes: Synthesis of Enantiopure α‐ or β‐Substituted Vinylphosphane Oxides

Regioselective Metal‐Catalyzed Hydrophosphinylation of Alkynes: Synthesis of Enantiopure α‐ or β‐Substituted Vinylphosphane Oxides

Synthesis of Enantiopure 1‐r‐Alkyl‐2‐c,5‐t‐Diphenylphospholanes and Phospholanium Salts through Direct Alkylation of Phospholane

Enantioselective Hydrogenation of Enamines with Monodentate Phosphorus Ligands

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