Single-Step Stereoselective Synthesis of (E)- and (Z)-Allylamines from Acetyl Derivatives of Baylis-Hillman Adducts [1]

Abstract

Stereoselective synthesis of (E)- and (Z)-allylamines has been achieved in a single-step by treatment of the acetyl derivatives of Baylis-Hillman adducts with ammonium acetate in anhydrous methanol at room temperature. The reaction proceeded under neutral conditions to form the corresponding allylamines in high yields and stereoselectivity.

Key words

allylamine - Baylis-Hillman adduct - acetyl derivative - NH₄OAc - stereochemistry

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Part 56 in the series, ‘Studies on Novel Synthetic Methodologies’. IICT Communication No. 050216

References

• 2a Baylis AB, and Hillman MED. inventors; German Patent  2155113.  ; Chem. Abstr. 1972, 77, 34174q
• 2b Basavaiah D. Rao AJ. Satyanarayana T. Chem. Rev.  2003,  103:  811 ; and references cited therein
• 3a Hoffmann HMR. Rabe J. Angew. Chem., Int. Ed. Engl.  1985,  24:  94 
• 3b Buchholz R. Hoffmann HMR. Helv. Chim. Acta  1991,  74:  1213 
• 4a Das B. Banerjee J. Ravindranath N. Venkataiah B. Tetrahedron Lett.  2004,  45:  2425 
• 4b Das B. Banerjee J. Ravindranath N. Tetrahedron  2004,  60:  8357 
• 4c Das B. Banerjee J. Mahender G. Majhi A. Org. Lett.  2004,  6:  3349 
• 4d Das B. Banerjee J. Majhi A. Mahender G. Tetrahedron Lett.  2004,  45:  9225 
• 5a Ma J. Angew. Chem. Int. Ed.  2003,  42:  4290 
• 5b Chowdari NS. Suri JT. Barbas CF. Org. Lett.  2004,  6:  2507 
• 6 Ramesh C. Mahender G. Ravindranath N. Das B. Tetrahedron  2003,  59:  1049 
• 7 Tanemura K. Suzuki T. Nishida Y. Satsumabayashi K. Horaguchi T. Chem. Commun.  2004,  470 
• 9a Larson GL. de Kaifer CF. Seda R. Torres LE. Ramirez JR. J. Org. Chem.  1984,  49:  3385 
• 9b Basavaiah D. Sarma PKS. Bhavani AKD. J. Chem. Soc., Chem. Commun.  1994,  1091 
• 9c Baraldi PG. Guarneri M. Pollini GP. Simoni D. Barco A. Benetti S. J. Chem. Soc., Perkin Trans. 1  1984,  2501 
• 9d Tanaka K. Yamagishi N. Tanikaga R. Kaji A. Bull. Chem. Soc. Jpn.  1979,  52:  3619 
• 9e Minami I. Yahara M. Shimizu I. Tsuji J. J. Chem. Soc., Chem. Commun.  1986,  118 
• 9f Oda M. Yamamura A. Watabe T. Chem. Lett.  1979,  8:  1427 
• 9g Matsuda I. Okada H. Izumi Y. Bull. Chem. Soc. Jpn.  1983,  56:  528 
• 9h Boche G. Buckl K. Martens D. Schneider DR. Tetrahedron Lett.  1979,  19:  4967 
• 10a Foucaud A. El Guemmout F. Bull. Chim. Soc. Fr.  1989,  403 
• 10b Patra A. Roy AK. Batra S. Bhaduri AP. Synlett  2002,  1819 

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Part 56 in the series, ‘Studies on Novel Synthetic Methodologies’. IICT Communication No. 050216

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General Procedure for the Preparation of Allylamines.
To a solution of 1 or 2 (1 mmol) in anhyd MeOH (10 mL), NH₄OAc (8 equiv) was added in one portion under a nitrogen atmosphere. The mixture was stirred at r.t. and monitored by TLC. After completion, the solution was concentrated and dissolved in CH₂Cl₂ (10 mL). The solution was washed with brine (3 × 10 mL) followed by H₂O (3 × 10 mL) and the combined aqueous washings extracted with CH₂Cl₂ (3 × 10 mL). The total CH₂Cl₂ portion was concentrated and subjected to column chromatography over silica gel using EtOAc-hexane (1:4) as eluent to afford pure allylamine (3 or 4). The spectroscopic and analytical data of some representative allylamines (major product) are given below.
Compound 3b: IR (KBr): ν_max = 3452, 1722, 1526, 1482 cm^-1. ¹H NMR (200 MHz, CDCl₃): δ = 7.92 (1 H, s), 7.46 (1 H, dd, J = 8.0, 2.0 Hz), 7.34 (1 H, dd, J = 8.0, 2.0 Hz), 7.22 (1 H, td, J = 8.0, 2.0 Hz), 7.12 (1 H, td, J = 8.0, 2.0 Hz), 3.74 (3 H, s), 3.10 (2 H, s). ¹³C NMR (50 MHz, CDCl₃): δ = 168.4, 139.7, 134.0, 133.5, 131.6, 131.2, 129.8, 129.4, 126.6, 52.0, 49.6. EIMS: m/z = 225, 227 [M⁺]. Anal. Calcd for C₁₁H₁₂ClNO₂ (%): C, 58.54; H, 5.32; N, 6.21. Found: C, 58.62; H, 5.29; N, 6.28.
Compound 3d: IR (KBr): ν_max = 3462, 1723, 1585, 1505 cm^-1. ¹H NMR (200 MHz, CDCl₃): δ = 8.40 (1 H, t, J = 2.0 Hz), 8.18 (1 H, dt, J = 8.0, 2.0 Hz), 7.82 (1 H, dt, J = 8.0, 2.0 Hz), 7.80 (1 H, s), 7.54 (1 H, t, J = 8.0 Hz), 3.83 (3 H, s), 3.54 (2 H, s). ¹³C NMR (50 MHz, CDCl₃): δ = 167.8, 148.3, 140.0, 136.4, 135.6, 129.6, 135.3, 124.3, 123.4, 52.2, 50.1. MS (EI): m/z = 236 [M⁺]. Anal. Calcd for C₁₁H₁₂N₂O₄ (%): C, 55.93; H, 5.08; N, 11.86. Found: C, 55.88; H, 5.01; N, 11.84.
Compound 3e: IR (KBr): ν_max = 3440, 1732, 1560, 1522 cm^-1. ¹H NMR (200 MHz, CDCl₃): δ = 6.89 (1 H, t, J = 7.0 Hz), 3.64 (3 H, s), 3.08 (2 H, s), 2.09 (2 H, t, J = 7.0 Hz), 1.72 (1 H, m), 0.92 (6 H, d, J = 7.0 Hz). MS (EI): m/z = 171 [M⁺]. Anal. Calcd for C₉H₁₇NO₂ (%): C, 63.17; H, 15.74; N, 12.96. Found: C, 63.24; H, 15.81; N, 12.85.
Compound 4a: IR (KBr): ν_max = 3453, 2354, 1620, 1532 cm^-1. ¹H NMR (200 MHz, CDCl₃): δ = 7.72-7.67 (2 H, m), 7.40-7.28 (3 H, m), 7.07 (1 H, s), 3.56 (2 H, s). ¹³C NMR (50 MHz, CDCl₃): δ = 137.2, 130.5, 129.9, 129.4, 128.6, 128.3, 126.2, 118.8, 116.5, 52.0. MS (EI): m/z = 158 [M⁺]. Anal. Calcd for C₁₀H₁₀N (%): C, 83.33; H, 6.94; N, 19.44. Found: C, 83.41; H, 6.88; N, 19.40.
Compound 4c: IR (KBr): ν_max = 3442, 2352, 1522, 1485 cm^-1. ¹H NMR (200 MHz, CDCl₃): δ = 7.72 (2 H, d, J = 8.0 Hz), 7.43 (2 H, d, J = 8.0 Hz), 7.10 (1 H, s), 3.62 (2 H, s). MS (EI): m/z = 192, 194 [M⁺]. Anal. Calcd for C₁₀H₉ClN₂ (%): C, 62.34; H, 4.68; N, 14.55. Found: C, 62.41; H, 4.71; N, 14.51.