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Synlett 2010(19): 2895-2898  
DOI: 10.1055/s-0030-1259030
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Mechanochemical Diels-Alder Cycloaddition Reactions for Straightforward Synthesis of endo-Norbornene Derivatives

Ze Zhang*, Zhi-Wei Peng, Ming-Feng Hao, Jian-Gang Gao
School of Biochemical Engineering, Anhui Polytechnic University, Wuhu, Anhui 241000, P. R. of China
Fax: +86(553)2871254; e-Mail: zzhang@ahpu.edu.cn;
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Publication History

Received 16 August 2010
Publication Date:
10 November 2010 (online)

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Abstract

Under mechanochemical milling conditions, Diels-­Alder cycloaddition of cyclopentadiene with maleic anhydride and maleimide derivatives proceeded very smoothly, affording endo-norbornenes exclusively in quantitative yield. All the transformations were accomplished at room temperature without using any catalyst or organic solvent, thus the workup and purification procedure is very simple. Control experiments on traditional and other tentative conditions were also investigated.

Key words

norbornenes - mechanochemical milling - solvent-free - cyclopentadiene - Diels-Alder reaction

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Analytical Data for Representative Compound
endo -4-(4-Bromophenyl)-4-aza-tricyclo[5.2.1.0 ²,6 ]dec-8-ene-3,5-dione (3e) Mp 156-157 ˚C. IR (KBr): 2954, 2926, 1711, 1466, 1090, 904, 736, 610 cm-¹. ¹H NMR (400 MHz, CDCl3): δ = 1.59 (d, J = 8.8 Hz, 1 H), 1.78 (d, J = 8.8 Hz, 1 H), 3.30 (t, J = 8.8 Hz, 2 H), 3.41-3.49 (m, 2 H), 6.24 (s, 2 H), 7.02 (d, J = 8.8 Hz, 2 H), 7.53 (d, J = 8.8 Hz, 2 H). ¹³C NMR (100 MHz, CDCl3): δ = 45.5, 45.8, 52.2, 122.4, 128.1, 130.7, 132.2, 134.6, 176.4. HRMS (FAB+): m/z calcd for C15H12BrNO2 [M+]: 317.0051; found: 317.0049.