A practical synthetic approach to chiral α-aryl substituted ethylphosphonates

Goulioukina, Natalia S; Dolgina, T. M.; Beletskaya, I. P.; Henry, Jean‐Christophe; Lavergne, Damien; Ratovelomanana‐Vidal, Virginie; Genêt, Jean‐Pierre

doi:10.1016/s0957-4166(01)00031-3

Cited by 81 publications

(31 citation statements)

References 47 publications

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“…60 We succeeded in performing asymmetric reduction using catalysis with ruthenium complexes containing chiral ligands; of these, (R)-MeO-Biphep was found to be the best (Scheme 25). 61 However, the highest optical yields were reached with a phosphine-oxazoline cationic iridium complex (Pflatz catalyst) (Scheme 26). Note that the enantiomeric purity was as high as 95% for the P-analogue of Naproxen.…”

Section: Addition Of Compounds With a P-h Bond (Phosphines And Dialkymentioning

confidence: 99%

Catalytic synthesis and transformations of organophosphorus compounds

Beletskaya

Kabachnik

2008

Mendeleev Communications

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Section: Addition Of Compounds With a P-h Bond (Phosphines And Dialkymentioning

confidence: 99%

Catalytic synthesis and transformations of organophosphorus compounds

Beletskaya

Kabachnik

2008

Mendeleev Communications

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“…Noyori and coworkers reported that ␣-substituted ␤-ketophosphonates were subjected to enantio-and diastereoselective hydrogenation by the use of the BINAP-Ru(II) complex to give the corresponding ␤-hydroxyphosphonates with exceedingly high ee's (94-98%) (23,24). Also worth mentioning is that optically active ␣-arylsubstituted ethylphosphonates, phosphorus analogs of 2-arylpropionic acids, were produced by Ir-and Ru-catalyzed asymmetric hydrogenation of ethenylphosphonates (25,26).On the other hand, we previously designed and synthesized new bidentate phosphine ligands, (S,S)-1,2-bis(alkylmethylphosphino)ethanes (alkyl ϭ tert-butyl, 1,1-diethyl-propyl, 1-adamantyl, 1-methylcyclohexyl, cyclohexyl, cyclopentyl, and isopropyl) (BisP*) (27) and (R,R)-bis(alkylmethylphosphino)methanes (alkyl ϭ tert-butyl, cyclohexyl, isopropyl, and phenyl) (MiniPHOS) (28). An important feature of these ligands is that a bulky alkyl group and the smallest alkyl group (methyl group) are bound to each phosphorus atom.…”

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confidence: 99%

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confidence: 99%

Asymmetric hydrogenation of α,β-unsaturated phosphonates with Rh-BisP* and Rh-MiniPHOS catalysts: Scope and mechanism of the reaction

Gridnev

Yasutake

Imamoto

et al. 2004

Proc. Natl. Acad. Sci. U.S.A.

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Optically active 1,2-bis(alkylmethylphosphino)ethanes and bis(alkylmethylphosphino)methanes are unique diphosphine ligands combining the simple molecular structure and P-stereogenic asymmetric environment. This work shows that these ligands exhibit excellent enantioselectivity in rhodium-catalyzed asymmetric hydrogenation of ␣,␤-unsaturated phosphonic acid derivatives. The enantioselective hydrogenation mechanism elucidated by NMR study is also described. The ␣-hydroxy-and ␣-aminophosphonic acids have an extremely rich and varied spectrum of biological activity (1, 2) that is stipulated by their ability to act as antagonists for amino acids inhibiting enzymes involved in the amino acids' metabolism. They can be used as herbicides (3, 4), antiviral drugs (5), antibiotics (6), and neurodrugs (7). Being able to affect the biological activity of cells (8), some of them can inhibit HIV protease (9) and alanine racemase (alafosfalin) (10). Peptide ␣-hydroxyphosphonates are known to be rennin inhibitors (11).The biological activity of the phosphonic acids highly depends on the absolute configuration of its ␣-chiral center. An excellent example is alafosfalin, [N-(L-alanyl)-L-1-aminoethyl]phosphonic acid (S,R)-diastereomer. Only this diastereomer unlike (R,R)-, (S,S)-, and (R,S)-diastereomers shows high antibacterial activity (12, 13).Development of the synthesis of optically active ␣-hydroxyand ␣-aminophosphonic acids has begun only recently (2, 15). ʈ Processes applying the catalytic amounts of the source of chirality are especially attractive. Thus, hydrophosphonylation of imines catalyzed by heterobimetallic complexes Ln-K-BINOL (16) and hydrophosphonylation of aldehydes catalyzed by analogous complexes Al-Li-BINOL (17) give the ␣-amino-and ␣-hydroxyphosphonic acids, respectively, with high enantiomeric excesses (ee's). Furthermore, the catalytic asymmetric Michael addition to ␣,␤-unsaturated phosphonates (18, 19) and the allylation reaction of ␣-acetylamino-␤-ketophosphonates (20) have been successfully used for the synthesis of phosphonic acid derivatives with the stereogenic centers in the ␣-or ␤-position.Another convenient approach to the synthesis of the acids is the asymmetric hydrogenation of the corresponding unsaturated precursors. By this means, the phosphorus analogs of ␣-aminoor ␣-hydroxycarboxylic acids were obtained with up to 96% ee by using the Rh complexes of chiral phosphine ligands such as (Ϫ)-BPPM (2S,4S) (21) and DuPHOS (22). Noyori and coworkers reported that ␣-substituted ␤-ketophosphonates were subjected to enantio-and diastereoselective hydrogenation by the use of the BINAP-Ru(II) complex to give the corresponding ␤-hydroxyphosphonates with exceedingly high ee's (94-98%) (23,24). Also worth mentioning is that optically active ␣-arylsubstituted ethylphosphonates, phosphorus analogs of 2-arylpropionic acids, were produced by Ir-and Ru-catalyzed asymmetric hydrogenation of ethenylphosphonates (25,26).On the other hand, we previously designed and synthesized new bidentate phosphine ligands, (S,S...

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“…[2,3] In particular, many efforts have been devoted to the development of the metal-catalyzed synthetic protocols. In addition to transition-metal-catalyzed C-P bond formation reactions, [4][5][6] C-C cross-coupling reactions employing alkenyl or aryl halides as the electrophilic coupling partners have become an alternative and/or complementary route. [7] However, the difficult preparation and purification of α-bromoalkenylphosphonates and alkenyl boronophosphonates with well-defined stereochemistry make these procedures less attractive.…”

Section: Introductionmentioning

confidence: 99%