Synlett 2012; 23(12): 1765-1768
DOI: 10.1055/s-0031-1289785
letter
© Georg Thieme Verlag Stuttgart · New York

Diastereoselectivity in Diels–Alder Cycloadditions of Erythrose Benzylidene-acetal 1,3-Butadienes with Maleimides

Daniela A. L. Salgueiro
Departamento de Química, Universidade do Minho, Campus de Gualtar, 4710-057 Braga, Portugal
,
Vera C. M. Duarte
Departamento de Química, Universidade do Minho, Campus de Gualtar, 4710-057 Braga, Portugal
,
Cristina E. A. Sousa
Departamento de Química, Universidade do Minho, Campus de Gualtar, 4710-057 Braga, Portugal
,
Maria J. Alves*
Departamento de Química, Universidade do Minho, Campus de Gualtar, 4710-057 Braga, Portugal
,
António Gil Fortes
Departamento de Química, Universidade do Minho, Campus de Gualtar, 4710-057 Braga, Portugal
› Author Affiliations
Further Information

Publication History

Received: 12 March 2012

Accepted after revision: 07 May 2012

Publication Date:
22 June 2012 (online)


Abstract

Maleimides were combined with d-erythrose benzylidene-acetal 1,3-butadienes to study the facial selectivity of the Diels–Alder cycloadditions. The selectivity was found to range from moderate to good. The reaction diastereotopicity can be reversed with the temperature. Simultaneous coordination of the diene, having a free hydroxy group, and maleimide to a chiral bimetallic Lewis acid catalyst (LACASA–DA reaction) occurs with complete diastereocontrol to give a single adduct, using an extra chiral inductor either (R)- or (S)-BINOL.

 
  • References and Notes

  • 1 Mukhopadhyay A, Ali SM, Husain M, Suryawanshi SN, Bhakuni DS. Tetrahedron Lett. 1989; 30: 1853
  • 2 Alves MJ, Duarte VC. M, Faustino H, Gil Fortes A. Tetrahedron: Asymmetry 2010; 21: 1817
    • 3a Jones DW. J. Chem. Soc., Chem. Commun. 1980; 739
    • 3b Fisher MJ, Hehre WJ, Kahn SD, Overman LE. J. Am. Chem. Soc. 1988; 110: 4625
    • 3c Trost BM, Lee DC. J. Org. Chem. 1989; 54: 2271
    • 3d Macaulay JB, Fallis AG. J. Am. Chem. Soc. 1988; 110: 4074
    • 3e Macaulay JB, Fallis AG. J. Am. Chem. Soc. 1990; 112: 1136
    • 3f Tripathy R, Carrol PJ, Thornton ER. J. Am. Chem. Soc. 1990; 112: 6743
    • 3g Tripathy R, Carrol PJ, Thornton ER. J. Am. Chem. Soc. 1991; 113: 7630
  • 4 Analytical Data for Some Typical Compounds Compound 5a: [α]D 20 –92.4 (c 0.45, EtOAc). IR (Nujol): νmax = 3441, 1690, 1457 cm–1. 1H NMR (400 MHz, CDCl3): δ = 2.22–2.32 (1 H, m, H-7), 2.75–2.90 (2 H, m, H-7 and H-3a), 3.35 (1 H, tdd, J = 11.6, 5.8, 3.5 Hz, H-4), 3.60 (1 H, td, J = 11.2, 0.8 Hz, H-6′), 3.83 (1 H, br s, H-5′), 3.96 (1 H, dt, J = 15.0, 7.5 Hz, H-7a), 4.28 (1 H, t, J = 9.0 Hz, H-4′), 4.36 (1 H, ddd, J = 11.0, 5.1, 2.3 Hz, H-6′), 5.52 (1 H, s, H-2′), 6.02–6.13 (1 H, m, H-6), 6.17 (1 H, dt, J = 9.4, 3.2 Hz, H-5), 7.11–7.18 (2 H, m, Ph), 7.32–7.54 (8 H, m, Ph) ppm. 13C NMR (100 MHz, CDCl3): δ = 24.27 (C-7), 39.23 (C-3a), 40.41 (C-4), 41.43 (C-7a), 66.44 (C-5′), 71.89 (C-6′), 80.46 (C-4′), 101.10 (C-2′), 126.06 (C-H, Ph), 126.42 (C-H, Ph), 128.13 (C-6), 128.23 (C-H, Ph), 128.83 (C-H, Ph), 128.94 (C-H, Ph), 129.12 (C-H, Ph), 130.14 (C-5), 131.56 (Cq, Ph), 137.49 (Cq, Ph), 178.53 (C=O), 179.81 (C=O) ppm. ESI-HRMS: m/z calcd for C24H23NNaO5: 428.1467; found: 428.1468. Compound 6a: [α]D 20 –118.2 (c 0.45, EtOAc). IR (Nujol): νmax = 3442, 1690, 1411, 1072 cm–1. 1H NMR (400 MHz, CDCl3): δ = 2.17–2.31 (1 H, m, H-7), 2.64–2.76 (1 H, m, H-4), 2.83 (1 H, ddd, J = 15.4, 7.0, 1.6 Hz, H-7), 3.27 (1 H, td, J = 8.0, 1.6 Hz, H-3a), 3.65 (1 H, t, J = 10.4 Hz, H-6′), 3.81 (2 H, dd, J = 9.0, 5.5 Hz, H-7a and H-5′), 4.27 (1 H, dd, J = 10.8, 5.1 Hz, H-6′), 4.44 (1 H, t, J = 9.6 Hz, H-4′), 5.64 (1 H, s, H-2′), 6.02 (1 H, ddt, J = 12.9, 6.5, 3.3 Hz, H-6), 6.41 (1 H, dt, J = 9.4, 3.5 Hz, H-5), 7.19–7.22 (2 H, m, Ph), 7.35–7.40 (4 H, m, Ph), 7.43–7.47 (2 H, m, Ph), 7.50–7.52 (2 H, m, Ph) ppm. 13C NMR (100 MHz, CDCl3): δ = 25.00 (C-7), 39.50 (C-3a), 40.09 (C-7a), 41.32 (C-4), 68.05 (C-5′), 71.24 (C-6′), 79.47 (C-4′), 100.79 (C-2′), 126.08 (C-H, Ph), 126.54 (C-H, Ph), 127.54 (C-6), 128.19 (C-H, Ph), 128.60 (C-H, Ph), 128.85 (C-H, Ph), 129.08 (Cq, Ph), 130.62 (C-5), 131.89 (Cq, Ph), 137.70 (Cq, Ph), 177.21 (C=O), 179.05 (C=O) ppm. ESI-HRMS: m/z calcd for C24H23NNaO5: 428.1473; found: 428.1468
  • 5 Compound 5a: H-5: 6.40 (dt, J = 3.2, 9.2 Hz); H-2′: 5.64 (s). Compound 5b: H-5: 6.38 (dt, J = 3.6, 9.2 Hz); H-2′: 5.66 (s). Compound 5c: H-5: 6.34 (dt, J = 3.6, 9.2 Hz); H-2′: 5.67 (s). Compound 5d: H-5: 6.28 (dt, J = 3.6, 9.2 Hz); H-2′: 5.67 (s). Compound 6a: H-5: 6.17 (dt, J = 3.2, 9.2 Hz); H-2′: 5.51 (s). Compound 6b: H-5: 6.12 (dt, J = 3.6, 9.6 Hz); H-2′: 5.54 (s). Compound 6c: H-5: 6.16 (br s),* H-2′: 5.42 (s). Compound 6d: H-5: 6.08 (br t, 2.0 Hz),* H-2′: 5.42 (s). * These signals coincide with H-6
    • 6a Ding X, Ukaji Y, Fujinami S, Inomata K. Chem. Lett. 2003; 32: 582
    • 6b Ukaji Y, Inomata K. Synlett 2003; 1075
    • 7a Ward DE, Souweha MS. Org. Lett. 2005; 3533
    • 7b Ward DE, Mohammad SA. Org. Lett. 2000; 3937
  • 8 Preparation of Solution A A solution of diene 1 (0.05 g, 0.22 mmol) in dry toluene (1.0 mL) was added to a solution of Me2Zn (1.2 M) in toluene (178 μL, 0.22 mmol) at 0 °C and stirred for 5 min. Preparation of Solution B A solution of (S)-BINOL (0.061 g; 0.22 mmol) in dry toluene (1.0 mL) was added to a solution of MeMgBr (1.4 M in toluene–THF; 152 μL, 0.22 mmol) at 0 °C and stirred for 5 min. Solution A was added to solution B, the mixture diluted with dry toluene (1.8 mL) and stirred for 5 min. This mixture was refrigerated at –78 °C and a solution of maleimide (3; 0.02 g, 0.22 mmol) in dry toluene (1.5 mL) was then added. The temperature was allowed to rise gradually to r.t. The reaction was complete after 17 d and was quenched with an aq sat. solution of NaHCO3 (1 mL), filtered through a pad of Celite, and the Celite was washed with EtOAc (4 × 10 mL). The filtrates were combined and concentrated under reduced pressure to give a yellow oil that was submitted to ‘dry-flash’ chromatography using a mixture of PE (40–60)–Et2O. (S)-BINOL was recovered (0.035 g, 57%) from PE–Et2O (1:1), and the product was eluted with PE–Et2O (1:2.3; 0.024 g, 33%)