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Synlett 2002(9): 1471-1474
DOI: 10.1055/s-2002-33529
LETTER
© Georg Thieme Verlag Stuttgart · New York

Stereoselective Synthesis of β-Amino-α-hydroxy(allyl)phosphinates and an Application to the Synthesis of a Building Block for Phosphinyl Peptides

Takehiro Yamagishi, Takanori Kusano, Tsutomu Yokomatsu*, Shiroshi Shibuya
School of Pharmacy, Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Fax: +81(426)763239; e-Mail: yokomatu@ps.toyaku.ac.jp;
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Publication History

Received 1 July 2002
Publication Date:
17 September 2002 (online)

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Abstract

Hydrophosphinylation of N,N-dibenzyl-α-amino aldehydes with ethyl allylphosphinate in the presence of (S)-ALB afforded anti-β-amino-α-hydroxy(allyl)phosphinates in high diastereoselectivity. The hydrophosphinylation product was transformed to a potentially useful transition state mimic for hydrolysis of dipeptides.

Key words

phosphorus - amino aldehyde - β-amino-α-hydroxy(allyl)phosphinates - hydrophosphinylation - diastereoselectivity

    References

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10

Genaral Procedure for the Hydrophosphinylation of 3a-c in the Presence of ( S )-ALB. To a solution of ethyl allylphosphinate (804 mg, 6.0 mmol) in THF (4 mL) was added 0.1 M THF solution of (S)-ALB (8 mL, 0.8 mmol), prepared from (S)-BINOL (458 mg, 1.6 mmol) and LiAlH4 (30.4 mg, 0.8 mmol) in situ, and a solution of 2a-c (4.0 mmol) in THF (8 mL) at 0 °C under stirring. After being stirred for 12 h at the same temperature, the mixture was diluted with H2O and extracted with CHCl3. The combined extracts were washed with brine and dried over MgSO4. Removal of solvent gave a residue, which was chromatographed on silica gel (hexane-EtOAc = 2:1) to give syn-3a-c and anti-3a-c.
syn-3a. This compound was obtained as a mixture of diastereomers arising from the chirality of the phosphorus atom in a ratio of 1:1.6. Mp 87-89 °C; 1H NMR (400 MHz, CDCl3) δ 7.42-7.20 (15 H, m), 5.91-5.79 (0.5 H, m), 5.58-5.46 (0.5 H, m), 5.28-5.21 (1 H, m), 4.93-4.88 (1 H, m), 4.16-4.12 (2 H, m), 3.84-3.59 (3 H, m), 3.53-3.43 (2 H, m), 3.04-2.94 (1 H, m), 2.82-2.60 (1 H, m), 2.44-2.34 (0.5 H, m), 2.25-2.16 (0.5 H, m), 1.34 (3 H, t, J = 7.0 Hz); 31P NMR (162 MHz, CDCl3) δ 52.35, 50.21; IR (KBr) 3215, 1046 cm-1; EIMS m/z 464 (MH+). Anal. calcd for C28H34NO3P: C, 72.55; H, 7.39. Found: C, 72.44; H, 7.25.
anti-3a. This compound was obtained as a mixture of diastereomers arising from the chirality of the phosphorus atom in a ratio of 1:1.1. Mp 168-170 °C; 1H NMR (400 MHz, CDCl3) δ 7.27-7.06 (15 H, m), 5.87-5.71 (1 H, m), 5.29-5.05 (2 H, m), 4.15-3.92 (3 H, m), 3.87 (2 H, d, J = 14.1 Hz), 3.59 (2 H, d, J = 14.1 Hz), 3.49-3.38 (1 H, m), 3.18-3.07 (2 H, m), 2.78-2.50 (2 H, m), 1.20 (3 H, t, J = 7.0 Hz), 1.18 (3 H, t, J = 7.0 Hz); 31P NMR (162 MHz, CDCl3) δ 49.18, 49.05; IR (KBr) 3259, 1033 cm-1; EIMS m/z 464 (MH+). Anal. calcd for C28H34NO3P: C, 72.55; H, 7.39. Found: C, 72.30; H, 7.35.
syn-3b. This compound was obtained as a mixture of diastereomers arising from the chirality of the phosphorus atom in a ratio of 1:1. Oil; 1H NMR (400 MHz, CDCl3) δ 7.33-7.28 (10 H, m), 5.88-5.77 (0.5 H, m), 5.58-5.46 (0.5 H, m), 5.25-4.86 (2 H, m), 4.13-4.05 (2 H, m), 3.88 (2 H, d, J = 13.1 Hz), 3.59 (2 H, d, J = 13.1 Hz), 3.53-3.46 (1 H, m), 3.28-3.14 (1 H, m), 2.77-2.56 (1 H, m), 2.39-2.11 (1 H, m), 2.11-2.04 (1 H, m), 1.83-1.67 (2 H, m), 1.31 (3 H, t, J = 7.0 Hz), 1.04-0.99 (6 H, m); 31P NMR (162 MHz, CDCl3) δ 51.75, 50.22; IR(neat) 3262, 1036 cm-1; EIMS m/z 430 (MH+). High resolution MS calcd for C25H37NO3P (MH+): 430.2511. Found: 430.2488.
anti-3b. This compound was obtained as a mixture of diastereomers arising from the chirality of the phosphorus atom in a ratio of 1:1.1. Mp 141-143 °C; 1H NMR (400 MHz, CDCl3) δ 7.35-7.20 (10 H, m), 5.91-5.76 (1 H, m), 5.30-5.15 (2 H, m), 4.22-3.91 (3 H, m), 3.88 (1 H, d, J = 13.6 Hz), 3.85 (1 H, d, J = 13.6 Hz), 3.53 (1 H, d, J = 13.6 Hz), 3.52 (1 H, d, J = 3.6 Hz), 3.22-3.11 (1 H, m), 2.82-2.39 (2 H, m), 1.80-1.70 (1 H, m), 1.40-1.29 (2 H, m), 1.24 (1.5 H, t, J = 7.0 Hz), 1.20 (1.5 H, t, J = 7.0 Hz), 0.91 (3 H, d, J = 6.7 Hz), 0.58 (1.5 H, d, J = 6.5 Hz), 0.55 (1.5 H, d, J = 6.5 Hz); 31P NMR (162 MHz, CDCl3) δ 50.05, 49.44; IR (KBr) 3278, 1033 cm-1; EIMS m/z 430 (MH+). Anal. calcd for C25H36NO3P: C, 69.91; H, 8.45. Found: C, 69.77; H, 8.28.

11

For improving the syn-diastereoselectivity, we also examined hydrophosphinylation of 2b using other types of binaphthol-modified heterobimetallic complexes [(R)-LPB [21] and (R)-GaLB [22] ]. However, the syn-selectivity was not observed. The (R)-LPB catalyzed reaction showed moderate anti-selectivity (syn-3b:anti-3b = 22:78). A poor anti-selectivity (syn-3b:anti-3b = 44:51) was observed with (R)-GaLB.

16

X-Ray crystal data of anti-3c-A were collected by a Mac-Science DIP Image plate diffractometer. The structure was solved by a direct method using SIR-97 [23] and refined with a full matrix least-squares method. [24] Molecular formula = C22H30NO3P, M r = 387.46, orthorhombic, space group = P212121, a = 8.454(5), b = 11.111(2), c = 23.484(10) Å, V = 2205.9(2) Å3, T = 296 K, Z = 4, D x = 1.167 Mg m-3, (Mo-Kα) = 0.71073 Å, µ = 0.145 mm-1, R = 0.050 over 2591 independent reflections.

17

Crystallographic data (excluding structure factors) for the X-ray crystal structure analysis reported in this paper have been deposited with the Cambridge Crystallographic Data Center (CCDC) as supplementary publication No. CCDC 187211. Copies of the data can be obtained, free of charge, on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK [fax:+44(1223)336033 or e-mail: deposit@ccdc.cam.ac.uk].

19

The PDC oxidation of 9 in DMF, followed by esterificaton afforded 10 in 7% yield.

20

11. Amorphous; [α]D 26 = -7.21 (c 0.67, MeOH); 1H NMR (400 MHz, CD3OD) δ 4.17 (1 H, dd, J = 5.3, 5.3 Hz), 3.73 (3 H, s), 3.69-3.54 (1 H, m), 3.23-3.00 (2 H, m), 1.87-1.59 (3 H, m), 1.00 (3 H, d, J = 5.9 Hz), 0.97 (3 H, d, J = 6.2 Hz); 31P NMR (162 MHz, CD3OD) δ 41.91; 13C NMR (100 MHz, CD3OD) δ 168.4, 68.9 (d, J PC = 119.5 Hz), 59.1, 53.0, 38.8, 36.0 (d, J PC = 81.7 Hz), 25.9, 23.5, 21.8; IR(neat) 3314, 2956, 1729, 1115 cm-1; FABMS m/z 254 (MH+). High resolution MS calcd for C9H21NO5P (MH+): 254.1157. Found: 254.1164.