Catalytic Asymmetric Synthesis of .alpha.-Amino Phosphonates Using Lanthanoid-Potassium-BINOL Complexes

Sasai, Hiroaki; Arai, Shigeru; Tahara, Yoshihiro; Shibasaki, Masakatsu

doi:10.1021/jo00126a003

Cited by 233 publications

(75 citation statements)

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“…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.…”

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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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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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“…It is interesting to note that, as one of the heterobimetallic asymmetric catalysts, the LanthaniodPotassium-BINOL complex was used in an effective asymmetric hydrophosphonylation of an imine with excellent, up to 96%, de values [21].…”

Section: Methodsmentioning

confidence: 99%

New strategy for the synthesis of functionalized phosphonic acids

Yuan

et al. 1997

Heteroat. Chem.

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“…由于 α-氨基膦酸衍生物被认为是 α-氨基酸的含磷类似物, 特别是手性 α-氨基膦酸衍生物比非手性物质具有更强的生物活性 [2] , 可作为抗生素 [3,4] 、除草剂 [5] [18] , SnI 2 [19] , MgClO 4 [20] , Al 2 O 3 [21] , F 3 CCH 2 OH [22] 等. 对于手性 α-氨基膦酸及其衍生物的催化对映选择性合成, 2007 年以前研究主要集中在亚胺双键的不对称氢膦酰化反应领域 [23] , 用手性金属配合物 [24] 和手性有机小分子, 如 Jacobsen 手性硫脲衍生物 [25] 、手性奎宁衍生物等作反应的催化剂 [26] . 而使用手性催化剂直接催化一锅不对称多组分 (1) Benzene, r.t. …”

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