Download PDF
Synlett 2008(8): 1260-1264  
DOI: 10.1055/s-2008-1072732
LETTER
© Georg Thieme Verlag Stuttgart · New York

Samarium Diiodide Induced Reductive Coupling of d-Threose- and d-Erythrose-Derived Nitrones with Methyl Acrylate

Juraj Reháka, Lubor Fišera*a, Gabriel Podolana, Jozef Ko˛íšekb, Lucia Perašínováb
a Institute of Organic Chemistry, Catalysis and Petrochemistry, Slovak University of Technology, Radlinskeho 9, 81237 Bratislava, Slovak Republic
Fax: +421(2)52968560; e-Mail: lubor.fisera@stuba.sk;
b Institute of Physical Chemistry and Chemical Physics, Slovak University of Technology, Radlinskeho 9, 81237 Bratislava, Slovak Republic
Further Information

Publication History

Received 4 February 2008
Publication Date:
16 April 2008 (online)

    Permissions and Reprints All articles of this category

Abstract

An application of the samarium diiodide promoted coupling between nitrones and methyl acrylate using nitrones derived from d-erythrose and d-threose is described. The reaction course of coupling is dependent on the structure of the starting chiral nitrone. The results show that the method has potential use in the preparation γ-N-hydroxylamino esters, pyrrolidinones, and pyrrolidines containing carbohydrate residues.

Key words

samarium - C-glycosyl nitrones - amino acids - pyrrolidinones - stereoselective synthesis

8

Typical Experimental Procedure for Samarium Diiodide Mediated Coupling A stirred and carefully deoxygenated solution of the corresponding nitrone (0.5 mmol) in dry THF (5 mL) was cooled to -78 °C under argon. Methyl acrylate and H2O were degassed by boiling under a stream of argon for 20 min. Methyl acrylate (0.7 mmol), H2O (4 mmol), and a solution of SmI2 (15 mL of 0.1 M in THF, 1.5 mmol) were then added. The temperature was kept at -78 °C until the reaction was judged to be complete by TLC (2 h), whereupon a sat. aq solution of Na2S2O3 (40 mL) was added. The mixture was extracted with EtOAc (4 × 30 mL) and the combined organic layers were washed with brine, dried over MgSO4, filtered, and concentrated in a rotatory evaporator. The residue was purified by silica gel column chromatography using EtOAc-hexanes (1:2).

9

Crystal Data
C22H35NO4Si, M = 405.60, orthorhombic, P212121, a = 7.800(2) Å, 13.749(3) Å, 22.468(5) Å, V = 2409.5(9) Å3, Z = 4, D x = 1.118 Mg m-3, µ (Mo-Kα) = 0.1220 mm-1, F(000) = 880, colorless block, 0.305 × 0.492 × 0.739 mm-3, 42540 diffractions measured (R int = 0.021), 4901 unique, wR2 = 0.0951, conventional R = 0.044 on I values of 4507 diffractions with I > 2.0 σ(I), (Δ/σ)max = 0.001, S = 1.160 for all data and 254 parameters. Unit cell determination and intensity data collection (θmax = 26.40o) were performed on a Gemini R diffractometer12 at 100 (1) K. Structure solution was direct methods13 and refinements were achieved by full-matrix least-squares method13 on F**2. Further details of the crystal structure investigation can be obtained from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge, CB2 1EZ, UK (CCDC deposition 677669).
Representative Data for Products Compound 12: [α]D 25 -19.3 (c 0.28, CHCl3); mp 59-61 °C. 1H NMR (300 MHz, CDCl3): δ = 1.46 (d, 3 H, J = 5.0 Hz, CHCH 3), 2.01-2.3 (m, 2 H, H-3), 2.51-2.71 (m, 2 H, H-2), 3.17 (dt, J = 6.1, 7.9 Hz, 1 H, H-4), 3.71 (s, 3 H, CO2CH3), 3.76 (s, 1 H, H-5′), 4.03 (d, J = 7.9 Hz, 1 H, H-4′), 4.07 (d, J = 13.1 Hz, 1 H, H-6′A), 4.14 (d, J = 13.1 Hz, 1 H, H-6′B), 3.80-4.20 (br s, 2 H, NOH, OH), 3.96-4.20 (dd, J = 12.2 Hz, 2 H, NCH 2Ph), 4.85 (q, J = 5.0 Hz, 1 H, H-2′), 7.36-7.51 (m, 5 H, NCH2 Ph) ppm. 13C NMR (75 MHz, CDCl3): δ = 20.9 (q, CHCH3), 22.0 (t, C-3), 32.2 (t, C-2), 51.6 (q, CO2 CH3), 61.3 (t, C-6′), 64.1 (d, C-5′), 64.5 (d, C-4), 71.8 (t, NCH2Ph), 79.8 (d, C-4′), 99.7 (d, C-2′), 127.2, 128.3, 129.0, 138.3 (3 d, s, NCH2 Ph), 175.1 (s, C-1) ppm. IR (KBr): ν = 3502, 3471, 3032, 3000, 2965, 2923, 2868, 2845, 1710 cm-1. Anal. Calcd for C17H25NO6 (339.3): C, 60.16; H, 7.42; N, 4.13. Found: C, 59.87; H, 7.41; N, 3.92.
Compound 13: [α]D 25 -19.8 (c 0.40, CHCl3). 1H NMR (300 MHz, CDCl3): δ = 1.29 (d, J = 5.2 Hz, 3 H, CHCH 3), 1.96-2.38 (m, 2 H, H-4), 2.24-2.63 (m, 2 H, H-3), 3.15-3.20 (br s, 1 H, OH), 3.42 (s, 1 H, H-5′), 3.59-3.67 (m, 2 H, H-5, H-4′), 3.74 (d, J = 12.0 Hz, 1 H, H-6′A), 3.98 (d, J = 12.0 Hz, 1 H, H-6′B), 4.49 (q, J = 5.2 Hz, 1 H, H-2′), 4.24-4.85 (d, d, J = 14.0 Hz, 2 H, NCH 2Ph), 7.23-7.32 (m, 5 H, NCH2 Ph) ppm. 13C NMR (75 MHz, CDCl3): δ = 20.7 (q, CHCH3), 21.2 (t, C-4), 29.9 (t, C-3), 45.1 (t, NCH2Ph), 58.7 (d, C-5), 64.4 (d, C-5′), 72.1 (t, C-6′), 77.4 (d, C-4′), 99.5 (d, C-2′) 127.3, 127.8, 128.3, 136.9 (3 d, s, CH2 Ph), 176.2 (s, C-2) ppm. IR (KBr): 3430, 3030, 2991, 2967, 2939, 2864, 1675 cm-1. Anal. Calcd for C16H21NO4 (291.3): C, 65.96; H, 7.27; N, 4.81. Found: C, 65.63; H, 7.22; N, 4.79.
Compound 16: [α]D 25 +9.4 (c 0.5, CHCl3); mp 93-95 °C. 1H NMR (300 MHz, CDCl3): δ = -0.03, 0.03 [2 s, 6 H, Si(CH 3)2C(CH3)3], 0.88 [s, 9 H, Si(CH3)2C(CH 3)3], 1.28 (d, J = 5.0 Hz, 3 H, CHCH 3), 1.87-2.05 (m, 1 H, H-4A), 2.25-2.38 (m, 1 H, H-3A), 2.53-2.74 (m, 2 H, H-3B, H-4B), 3.36 (d, J = 1.9 Hz, 1 H, H-5′), 3.49 (d, J = 8.9 Hz, 1 H, H-5), 3.61-3.66 (m, 1 H, H-6′A), 3.65 (s, 1 H, H-4′), 3.91-3.85 (dd, J = 1.0, 12.1 Hz, 1 H, H-6′B), 4.35 (q, J = 5.0 Hz, 1 H, H-2′), 4.34-4.71 (d, d, J = 15.3 Hz, 2 H, NCH 2Ph), 7.19-7.35 (m, 5 H, NCH2 Ph) ppm. 13C NMR (75 MHz, CDCl3): δ = -4.7, -4.6 [2 q, Si(CH3)2C(CH3)3], 17.9 [s, Si(CH3)2 C(CH3)3], 20.4 (t, C-4), 20.8 (q, CHCH3), 25.7 [q, Si(CH3)2C(CH3)3], 30.9 (t, C-3), 44.9 (t, NCH2Ph), 61.3 (d, C-5), 66.4 (d, C-5′), 72.1 (t, C-6′), 76.6 (d, C-4′), 98.8 (d, C-2′), 127.3, 127.4, 128.5, 136.8 (3 d, s, NCH2 Ph), 176.5 (s, C-2) ppm. IR (KBr): 3031, 2952, 2930, 2887, 2857, 1683
cm-1. Anal. Calcd for C22H35NO4Si (437.6): C, 65.15; H, 8.70; N, 3.45. Found: C, 65.34; H, 8.78; N, 3.25.
Compound 17: [α]D 25 +31.7 (c 0.45, CHCl3). 1H NMR (300 MHz, CDCl3): δ = 0.04, 0.12 [2 s, 6 H, Si(CH 3)2C(CH3)3], 0.92 [s, 9 H, Si(CH3)2C(CH 3)3], 1.35 (d, J = 5.0 Hz, 3 H, CHCH 3), 1.64-1.75 (m, 2 H, H-3), 1.79-1.90 (1 H, m, H-4A), 2.00-2.10 (m, 1 H, H-4B), 2.23-2.33 (m, 1 H, H-2A), 2.84-2.92 (1 H, m, H-2B), 2.96-3.04 (1 H, m, H-5), 3.28 (d, J = 7.3 Hz, 1 H, H-4′), 3.54 (d, J = 13.1 Hz, 1 H, NCH 2PhA), 3.72 (d, J = 11.9 Hz, 1 H, H-6′A), 3.79 (1 H, s, H-5′), 4.04 (d, J = 11.9 Hz, 1 H, H-6′B), 4.13 (d, J = 13.1 Hz, 1 H, NCH 2PhB), 4.72 (q, J = 5.0 Hz, 1 H, H-2′), 7.20-7.33 (m, 5 H, NCH2 Ph) ppm. 13C NMR (75 MHz, CDCl3): δ = -3.9, -3.7 [2 q, Si(CH3)2C(CH3)3], 18.4 [s, Si(CH3)2 C(CH3)3], 21.1 (q, CHCH3), 24.3 (t, C-3), 26.0 [q, Si(CH3)2C(CH3)3], 27.0 (t, C-4), 54.6 (t, C-2), 60.8 (t, NCH2Ph), 63.3 (d, C-5), 65.4 (d, C-5′), 71.7 (t, C-6′), 82.2 (d, C-4′), 99.2 (d, C-2′), 126.8, 128.2, 128.6, 140.2 (3 d, s, NCH2 Ph) ppm. IR (KBr): 2956, 2885, 2856, 2790, 1685, 1604 cm-1. Anal. Calcd for C22H37NO3Si (391.6): C, 67.47; H, 9.52; N, 3.58. Found: C, 67.47; H, 9.57; N, 3.36.
Compound 19: [α]D 25 +25.0 (c 0.2, CHCl3). 1H NMR (300 MHz, CDCl3): δ = 1.27 (d, J = 4.9 Hz, 3 H, CHCH 3), 1.93-2.31 (m, 2 H, H-3), 2.45-2.69 (m, 2 H, H-2), 2.96-3.04 (m, 1 H, H-4), 3.16-3.23 (m, 1 H, H-5′), 3.44-3.56 (m, 2 H, H-4′, H-6′A), 3.68 (s, 3 H, CO2CH 3), 3.91-3.96 (m, 1 H, H-6′B), 3.91-4.09 (2 d, J = 12.5 Hz, 2 H, NCH 2Ph), 4.58 (q, J = 4.9 Hz, 1 H, H-2′), 7.26-7.47 (m, 5 H, NCH2 Ph) ppm. 13C NMR (75 MHz, CDCl3): δ = 20.4 (q, CHCH3), 20.8 (t, C-3), 32.3 (t, C-2), 51.5 (q, CO2 CH3), 61.0 (t, C-6′), 67.4 (d, C-5′), 68.5 (d, C-4), 69.8 (t, NCH2Ph), 79.9 (d, C-4′), 99.1 (d, C-2′), 127.8, 128.6, 129.5, 136.6 (3 d, s, NCH2 Ph), 174.4 (s, C-1) ppm. IR (KBr): ν = 3362, 3063, 2994, 2967, 2950, 2881, 1728 cm-1. Anal. Calcd for C17H25NO6 (339.3): C, 60.16; H, 7.42; N, 4.13. Found: C, 60.09; H, 7.16; N, 3.79.
Compound 21: [α]D 25 -19.8 (c 0.05, CHCl3). 1H NMR (300 MHz, CDCl3): δ = 1.22 (d, J = 5.0 Hz, 3 H, CHCH 3), 1.89-2.15 (m, 2 H, H-4), 2.16-2.59 (m, 2 H, H-3), 3.24 (dd, J = 9.8, 11.2 Hz, 1 H, H-6′A), 3.46 (d, J = 9.6 Hz, 1 H, H-4′), 3.53 (dd, J = 5.1, 9.6 Hz, 1 H, H-5′), 3.59-3.79 (br s, 1 H, OH), 3.91-3.97 (m, 1 H, H-5), 4.03 (dd, J = 5.1, 11.2 Hz, 1 H, H-6′B), 4.25 (q, J = 5.0 Hz, 1 H, H-2′), 4.32-4.64 (dd, J = 15.3 Hz, 2 H, NCH 2Ph), 7.22-7.33 (m, 5 H, NCH2 Ph) ppm. 13C NMR (75 MHz, CDCl3): δ = 18.8 (t, C-4), 20.3 (q, CHCH3), 30.5 (t, C-3), 44.8 (t, NCH2Ph), 58.1 (d, C-5), 61.5 (d, C-5′), 70.8 (t, C-6′), 79.2 (d, C-4′), 98.6 (d, C-2′), 127.3, 127.8, 128.3, 136.8 (3 d, s, NCH2 Ph), 176.5 (s, C-2) ppm. IR (KBr): 3388, 3029, 2991, 2964, 2935, 2861, 1662 cm-1. Anal. Calcd for C16H21NO4 (291.3): C, 65.96; H, 7.27; N, 4.81. Found: C, 65.78; H, 7.38; N, 4.86.
Compound 23: [α]D 25 -23.8 (c = 0.34, CHCl3). 1H NMR (300 MHz, CDCl3): δ = 0.01, 0.03 [2 s, 6 H, Si(CH 3)2C(CH3)3], 0.81 [s, 9 H, Si(CH3)2C(CH 3)3], 1.31 (d, J = 5.1 Hz, 3 H, CHCH 3), 2.79 (dd, J = 8.1, 13.2 Hz, 1 H, CH 2NCH2PhA), 3.07 (dd, J = 2.1, 13.2 Hz, 1 H, CH 2NCH2PhB), 3.35 (t, J = 10.2 Hz, 1 H, H-6A), 3.53 (dt, J = 4.9, 9.3 Hz, 1 H, H-5), 3.71 (dt, J = 2.1, 9.3 Hz, 1 H, H-4), 3.80-3.92 (d, d, J = 13.2 Hz, 2 H, NCH 2Ph), 3.99 (dd, J = 4.9, 10.2 Hz, 1 H, H-6B), 4.67 (q, J = 5.1 Hz, 1 H, H-2), 6.12-6.31 (br s, OH), 7.22-7.38 (m, 5 H, NCH2 Ph) ppm. 13C NMR (75 MHz, CDCl3): δ = -4.9, -4.2 [2 q, Si(CH3)2C(CH3)3], 17.8 [s, Si(CH3)2 C(CH3)3], 20.5 (q, CHCH3), 25.6 [q, Si(CH3)2C(CH3)3], 59.9 (t, CH2NCH2Ph), 64.2 (d, C-5), 64.5 (t, NCH2Ph), 71.2 (t, C-6), 80.5 (d, C-4), 98.8 (d, C-2), 128.3, 128.9, 129.6, 136.8 (3 d, s, NCH2 Ph) ppm. IR (KBr): 3423, 3298, 3063, 3030, 2956, 2930, 2886, 2857, 1583, 1472, 1411 cm-1. Anal. Calcd for C19H33NO4Si (367.5): C, 62.09; H, 9.05; N, 3.81. Found: C, 62.16; H, 8.99; N, 3.52.
Compound 24: [α]D 25 +1.36 (c 0.22, MeOH). 1H NMR (300 MHz, CD3OD): δ = 1.01, 1.04 [2 s, 6 H, Si(CH 3)2C(CH3)3], 1.83 [s, 9 H, Si(CH3)2C(CH 3)3], 3.65 (t, J = 5.1 Hz, 2 H, H-2), 4.25-4.28 (br s, 1 H, OH), 4.34 (dd, J = 6.0, 11.2 Hz, 1 H, H-4B), 4.45 (dd, J = 5.1, 11.2 Hz, 1 H, H-4A), 4.96-5.01 (m, 1 H, H-3), 5.92 (s, 2 H, NCH 2Ph), 8.27 (t, 1 H, J = 5.1 Hz, H-1), 8.34-8.41 (m, 5 H, NCH2 Ph) ppm. 13C NMR (75 MHz, CD3OD): δ = -4.7, -4.3 [2 q, Si(CH3)2C(CH3)3], 18.9 [s, Si(CH3)2 C(CH3)3], 26.3 [q, Si(CH3)2C(CH3)3], 33.3 (t, C-2), 66.9 (t, C-4), 69.5 (t, NCH2Ph), 71.3 (d, C-3), 129.9, 130.1, 130.5, 134.4 (3 d, s, NCH2 Ph), 143.2 (C-1) ppm. IR (KBr): 3355, 2957, 2926, 2873, 1728, 1708, 1662 cm-1. Anal. Calcd for C17H29NO3Si (323.5): C, 63.12; H, 9.04; N, 4.33. Found: C, 62.94; H, 8.91; N, 4.01.

12

Oxford Diffraction (2007). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.