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

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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13

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.