Highly enantioselective hydrogenation of α,β-unsaturated phosphonates with iridium–phosphinooxazoline complex: synthesis of a phosphorus analogue of naproxen

Goulioukina, Natalia S; Dolgina, T. M.; Bondarenko, G. N.; Beletskaya, I. P.; Ilyin, M. M.; Davankov, V. A.; Pfaltz, Andreas

doi:10.1016/s0957-4166(03)00224-6

Cited by 59 publications

(29 citation statements)

References 14 publications

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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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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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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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“…In particular, arenephosphonates have shown biological activity both as Ca 2+ antagonists [2] and as cyclooxygenase inhibitors. [3] The majority of routes to generate non-racemic arenephosphonates have involved enantioselective hydrogenation of a,b-unsaturated phosphonates with rhodium-, [4] iridium-, [5] and rutheniumbased [6] catalysts. Whilst these methods have established the requisite chirality with very high selectivity, other strategies in which the C À P bond is installed as part of the asymmetric catalytic process have been less well studied and developed.…”

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A New Class of 3′‐Sulfonyl BINAPHOS Ligands: Modulation of Activity and Selectivity in Asymmetric Palladium‐Catalysed Hydrophosphorylation of Styrene

et al. 2008

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Palladium-catalysed monophosphorylation of (R)-2,2'-bisperfluoroalkanesulfonates of BINOL (R F = CF 3 or C 4 F 9 ) by a diaryl phosphinate [Ar 2 P(O)H] followed by phosphine oxide reduction (Cl 3 SiH) then lithium diisopropylamide-mediated anionic thia-Fries rearrangement furnishes enantio-Coupling of (R)-8a-j with (S)-1,1'-binaphthalene-2,2'-dioxychlorophosphine (S)-9 generates 3'-sulfonyl BINAPHOS ligands (R,S)-10a-j in good yields (43-82%). These new ligands are of utlility in the asymmetric hydrophosphonylation of styrene (1) by 4,4,5,5-tetramethyl-1,3,2-dioxaphospholane 2-oxide (2), for which a combination of the chiral ligands with either [Pd(+ /NaCHA C H T U N G T R E N N U N G (CO 2 Me) 2 proves to be a convenient and active pre-catalyst system. A combination of an electron-rich phosphine moiety and an electron-deficient 3'-sulfone moiety provides the best enantioselectivity to date for this process, affording the branched 2-phenethenephosphonate, (À)-iso-3, in up to 74% ee with ligand (R,S)-10i, where Ar = panisyl and the 3'-SO 2 R group is triflone.

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“…Since the first chiral mimic of Crabtrees complex was reported by Pfaltz and his coworkers, [8] many groups have contributed to an evergrowing bank of chiral N,P-ligated Ir complexes that work very well in olefin hydrogenation, but have only been tested with a limited range of substrates. [9,10] Recently, the demand for new, optically active chiral centers has encouraged us [11] and others [12] to test the Ir-catalyzed asymmetric hydrogenation of more Adv. Synth.…”

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Highly Selective Iridium‐Catalyzed Asymmetric Hydrogenation of Trifluoromethyl Olefins: A New Route to Trifluoromethyl‐ Bearing Stereocenters

et al. 2009

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Fluorine-containing compounds are useful in many applications ranging from pharmaceuticals to ferroelectric crystals. We have developed a new, highly enantioselective synthetic route to trifluoromethyl-bearing stereocenters in up to 96% ee via asymmetric hydrogenation using N,P-ligated iridium catalysts. We also hydrogenated an isomeric mixture of olefins; this reaction gave the hydrogenation product highly enantioselectively (87% ee), and only the E isomer was present after the reaction had reached 56% conversion.Keywords: asymmetric catalysis; fluorine; hydrogenation; iridium; P,N ligands Fluorine-containing compounds are useful in applications ranging from agrochemicals and pharmaceuticals to materials for liquid crystal displays (LCDs). [1] Among the fluoroorganic compounds, trifluoromethyl-substituted molecules have gained much attention, mainly because the electron-withdrawing ability of the trifluoromethyl group can significantly change the physical, chemical and biological properties of a compound. Therefore, much effort has been put towards the synthesis of CF 3 -bearing stereocenters, but their formation is still limited in scope. The existing syntheses of CF 3 -containing chiral centers rely mostly on chemical or biocatalytic resolutions of racemates or on the selective fluorination of chiral, non-fluorinated substrates. [2,3] Chiral Rh and Ru catalysts have been used in the asymmetric hydrogenation of CF 3 -substituted olefins. Because both types of catalysts require a coordinating group near the substrate double bond to obtain high enantioselectivity, all of the trifluoromethyl olefins hydrogenated so far have possessed functionality on or close to the double bond that bears the CF 3 group. In 1980, Koenig et al. reported the first successful asymmetric hydrogenation of a CF 3 -substituted olefin by applying a chiral Rh catalyst in the hydrogenation of 2-acetoxy-3,3,3-trifluoromethyl-1-propene with good enantioselectivity (77%).[4] Ten years later, Burk reported a higher ee (> 95%) for the reduction of the same substrate using Rh catalysts.[5] Kobayashi, Iseki and their co-workers enlarged the scope of functionalized trifluoromethyl olefin hydrogenation using a chiral Ru-(R)-BINAP catalyst.[6] They produced optically active 2-(trifluoromethyl)alkan-1-ols with ee values up to 83% and 2-(trifluoromethyl)propionic acid with 80% ee after derivatization; whereas they hydrogenated an unsaturated CF 3 -substituted ester to an almost racemic product. To the best of our knowledge, there are no routes to obtain simple chiral fluoroalkanes, because all methods give optically active fluoroalkanes with additional functionality.In the past decades, Ir complexes with chiral N,P ligands have proven to be efficient catalysts for the enantioselective hydrogenation of olefins.[7] As these catalysts hydrogenate both unfunctionalized and functionalized olefins, they have an advantage over Rh and Ru catalysts. Since the first chiral mimic of Crabtrees complex was reported by Pfaltz and his coworkers, [8] m...

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Highly enantioselective hydrogenation of α,β-unsaturated phosphonates with iridium–phosphinooxazoline complex: synthesis of a phosphorus analogue of naproxen

Cited by 59 publications

References 14 publications

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

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

A New Class of 3′‐Sulfonyl BINAPHOS Ligands: Modulation of Activity and Selectivity in Asymmetric Palladium‐Catalysed Hydrophosphorylation of Styrene

Highly Selective Iridium‐Catalyzed Asymmetric Hydrogenation of Trifluoromethyl Olefins: A New Route to Trifluoromethyl‐ Bearing Stereocenters

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