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

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.

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

References and Notes

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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) ų, 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 (θ_max = 26.40^o) 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.

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

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