Stereospecific Synthesis of Chalcogenoenynes by Palladium-Catalyzed Cross-Coupling Reaction

Gilson Zeni; Cristina W. Nogueira; Jesus M. Pena; Cristiane Pilissão; Paulo H. Menezes; Antonio L. Braga; João B. T. Rocha

doi:10.1055/s-2003-37519

LETTER

Stereospecific Synthesis of Chalcogenoenynes by Palladium-Catalyzed Cross-Coupling Reaction

Gilson Zeni*^a, Cristina W. Nogueira^a, Jesus M. Pena^a, Cristiane Pilissão^a, Paulo H. Menezes^b, Antonio L. Braga^a, João B. T. Rocha^a
^a Departamento de Química - Laboratório de Bioquímica Toxicológica -, UFSM 97105-900, Santa Maria, RS, Brazil
e-Mail: gzeni@quimica.ufsm.br;
^b Departamento de Química Fundamental, UFPE, Recife, PE, Brazil

Abstract

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Abstract

A new methodology for the synthesis of chalcogenoenynes is described. The palladium-catalyzed cross-coupling reaction of 1,2-bis(organanylchalcogeno)-alkenes and 1-alkynes gave the corresponding chalcogenoenynes in 71% to 88% yields. Preliminary pharmacologycal tests suggest that chalcogenoenynes may be useful drugs as anti-inflammatory and antinociceptive agents.

Key words

cross-coupling - chalcogenoenynes - palladium - tellurium - 1,2-bis(organanylchalcogeno)-alkenes

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References

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Pd(II) Catalyzed Cross-Coupling Reaction of 1,2-Bis(organanylchalcogeno)-alkenes 1a with 2-Propyn-1-ol; General Procedure: To a solution of PdCl₂ (20 mol%, 0.035 g), CuI (20 mol%, 0.038g) in MeOH (5 mL) at room temperature under argon atmosphere, were added 1a (0.327g, 1 mmol), 2-propyn-1-ol (0.112 g, 0.12 mL, 2 mmol) and Et₃N (0.8 mL). The mixture was stirred for the time indicated in Table [1] , treated with NH₄Cl saturated solution (5 mL) and then extracted with ethyl acetate. The organic layer was washed with brine and dried over MgSO₄. The solvent was evaporated and the residue was purified by flash silica-gel chromatography eluted with hexane/ethyl acetate (7:3) to yield 2b in 81% yield (0.16 g). ¹H NMR (200 MHz, CDCl₃) δ 6.09 (s, 1 H), 4.39(s, 2 H), 2.26 (s, 3 H), 2.06 (t, J = 7.0 Hz, 2 H,), 1.98 (s, 1 H), 1.43 (quint, J = 7.0 Hz, 2 H), 1.23-1.17 (m, 4 H), 0.88 (t, J = 6.5 Hz, 3 H); ¹³C NMR (50 MHz, CDCl₃) δ 134.51, 119.35, 94.97, 83.48, 51.54, 36.82, 31.03, 28.08, 22.35, 16.77, 13.92; IR (neat, cm^-1) ν 3363, 2921, 2214, 1660, 1436; LRMS (rel. int.) m/z 198 (30), 180 (44), 151 (100), 133 (17), 71 (83), 47 (38).