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

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

References

• 1 Tamao K. In Comprehensive Organic Synthesis   Vol. 3:  Trost BM. Fleming I. Pergamon; New York: 1991.  p.435-480  
• 2 Sonogashira K. Tohda Y. Hagihara N. Tetrahedron Lett.  1975,  4467 
• 3a Alami M. Linstrumelle G. Tetrahedron Lett.  1991,  32:  6109 
• 3b Alami M. Peyrat J.-F. Brion J.-D. Synthesis  2000,  1499 
• 4 Dieck HA. Heck FR. J. Orgmet. Chem.  1975,  93:  259 
• 5 Scott WJ. Peña MR. Sward K. Stoessel SJ. Stille JK. J. Org. Chem.  1985,  50:  2302 
• 6 Alami M. Crousse B. Ferri F. J. Orgmet. Chem.  2001,  624:  114 
• 7 Miyaura N. Yamada K. Suginome H. Suzuki A. J. Am. Chem. Soc.  1985,  107:  972 
• 8a Normant JF. Commerçon A. Villièras J. Tetrahedron Lett.  1975,  1465 
• 8b Alexakis A. Cahiez G. Normant JF. Synthesis  1979,  826 
• 9 Magriotis PA. Scott ME. Kim KD. Tetrahedron Lett.  1991,  32:  6085 
• 10 Negishi EI. Okukado N. King AO. Van Horn DE. Spiegel BI. J. Am. Chem. Soc.  1978,  100:  2254 
• 11 Dang HP. Linstrumelle G. Tetrahedron Lett.  1978,  19:  191 
• 12a Zeni G. Comasseto JV. Tetrahedron Lett.  1999,  40:  4619 
• 12b Zeni G. Menezes PH. Moro AV. Braga AL. Silveira CC. Stefani HA. Synlett  2001,  1473 
• 12c Zeni G. Nogueira CW. Panatieri RB. Silva DO. Menezes PH. Braga AL. Silveira CC. Stefani HA. Rocha JBT. Tetrahedron Lett.  2001,  42:  7921 
• 12d Zeni G. Lüdtke DS. Nogueira CW. Panatieri RB. Braga AL. Silveira CC. Stefani HA. Rocha JBT. Tetrahedron Lett.  2001,  42:  8927 
• 13a Barrientos-Astigarraga RE. Moraes DN. Comasseto JV. Tetrahedron Lett.  1999,  40:  265 
• 13b De Araujo MA. Comasseto JV. Synlett  1995,  1145 
• 13c Barrientos-Astigarraga RE. Castelani P. Comasseto JV. Formiga HB. Silva NC. Sumida CY. Vieira ML. J. Orgmet. Chem.  2001,  623:  43 
• 14a Mitchell TN. Wickenkamp R. Amamria A. Dieke R. Schneider U. J. Org. Chem.  1987,  52:  4868 
• 14b Sharma S. Oehlschlage AC. Tetrahedron Lett.  1986,  27:  6161 
• 14c Hibino JC. Matsubara S. Morizawa Y. Oshina K. Tetrahedron Lett.  1984,  25:  2151 
• 15 Mugesh G. Singh HB. Acc. Chem. Res.  2002,  35:  226 ; and references cited therein
• 16a Yoshida T. Negishi EI. J. Am. Chem. Soc.  1981,  103:  1276 
• 16b Negishi EI. Pure and Appl. Chem.  1981,  53:  2333 
• 17a Tucker CE. Knochel P. J. Am. Chem. Soc.  1991,  113:  9888 
• 17b Tucker CE. Greve B. Klein W. Knochel P. Organometallics  1994,  13:  94 
• 18 Lipshutz BH. Keil R. Barton JC. Tetrahedron Lett.  1992,  33:  5861 
• 19 Waas JR. Sidduri AR. Knochel P. Tetrahedron Lett.  1992,  33:  3717 
• 20a Pelter A. Colclough EM. Tetrahedron  1995,  51:  811 
• 20b Cooke MP. J. Org. Chem.  1994,  59:  2930 
• 21a Srebnik M. Deloux L. Sabat M. J. Org. Chem.  1995,  69:  3276 
• 21b Srebnik M. Deloux L. J. Org. Chem.  1994,  59:  6871 
• 21c Deloux L. Skrzypczac-Jankun E. Cheesman BV. Srebnik M. Sabat M. J. Am. Chem. Soc.  1994,  116:  10302 
• 22a Kolb M. Synthesis  1990,  171 
• 22b Silveira CC. Perin G. Braga AL. Tetrahedron Lett.  1995,  36:  7361 
• 22c Braga AL. Reckziegel A. Silveira CC. Comasseto JV. Synth. Commun.  1994,  24:  1165 
• 22d Dabdoub MJ. Cassol TM. Barbosa SL. Tetrahedron Lett.  1996,  37:  831 
• 22e Stefani HA. Comasseto JV. Petragnani N. Braga AL. Menezes PH. Gusevskaya EV. Phosphorus, Sulfur and Silicon  1997,  126:  211 
• 22f Dabdoub MJ. Begnini ML. Guerrero PG. Tetrahedron  1998,  54:  2371 
• 22g Denis JN. Desauvage S. Hevesi L. Krief A. Tetrahedron Lett.  1981,  22:  4009 
• 23 Braga AL. Zeni G. Silveira CC. Synlett  1997,  595 
• 24a Braga AL. Zeni G. Andrade LH. Silveira CC. Stefani HA. Synthesis  1998,  39 
• 24b Zeni G. Perin G. Cella R. Jacob RG. Braga AL. Silveira CC. Stefani HA. Synlett  2002,  6:  975 
• 25 Dabdoub MJ. Dabdoub VB. Pereira MA. Tetrahedron Lett.  2001,  1595 

26

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).