Stereoselective Synthesis of (Z)-1-Silyl-2-stannylethene by Palladium-­Catalyzed Silastannation of Ethyne and Its Synthetic Transformations

Abstract

(Z)-1-Silyl-2-stannylethenes were stereoselectively synthesized by silastannation of ethyne, catalyzed by a palladium/tert-alkyl isocyanide catalyst, and the synthetic utilities were demonstrated by their transformations.

Key words

palladium - alkyne - silylstannane - cis-addition - cross-coupling

References

• 1a Fleming I. Barbero A. Walter D. Chem. Rev.  1997,  97:  2063 
• 1b Colvin EW. Silicon Reagents in Organic Synthesis   Academic Press; London: 1988. 
• 1c Pereyre M. Quintard J.-P. Rahm A. Tin in Organic Synthesis   Butterworths; London: 1987. 
• 1d Davies AG. Organotin Chemistry   VCH; Weinheim: 1997. 
• 2 Cunico RF. Clayton FJ. J. Org. Chem.  1976,  41:  1480 
• 3a Graetz BR. Rychnovsky SD. Org. Lett.  2003,  5:  3357 
• 3b Beard RL. Klein ES. Standeven AM. Escobar M. Chandraratna RAS. Bioorg. Med. Chem. Lett.  2001,  11:  765 
• 3c Nakayama Y. Kumar GB. Kobayashi Y. J. Org. Chem.  2000,  65:  707 
• 3d Wu X.-D. Khim S.-K. Zhang Z. Cederstrom EM. Mariano PS. J. Org. Chem.  1998,  63:  841 
• 3e Corey EJ. Guzman-Perez A. Lazerwith SE. J. Am. Chem. Soc.  1997,  119:  11769 , and references therein
• 4a Barbero A. Cuadrado P. Fleming I. González AM. Pulido FJ. J. Chem. Soc., Chem. Commun.  1992,  351 
• 4b Barbero A. Cuadrado P. Fleming I. González AM. Pulido FJ. Rubio R. J. Chem. Soc., Perkin Trans. 1  1993,  1657 
• For palladium-catalyzed silastannation of alkynes see:
• 5a Mitchell TN. Killing H. Dicke R. Wickenkamp R. J. Chem. Soc., Chem. Commun.  1985,  354 
• 5b Chenard BL. Laganis ED. Davidson F. RajanBabu TV. J. Org. Chem.  1985,  50:  3666 
• 5c Chenard BL. Van Zyl CM. J. Org. Chem.  1986,  51:  3561 
• 5d Mitchell TN. Wickenkamp R. Amamria A. Dicke R. Schneider U. J. Org. Chem.  1987,  52:  4868 
• 5e Ritter K. Synthesis  1989,  218 
• 5f Casson S. Kocienski PJ. Reid G. Smith N. Street JM. Webster M. Synthesis  1994,  1301 
• 5g Lunot S. Thibonnet J. Duchêne A. Parrain J.-L. Abarbri M. Tetrahedron Lett.  2000,  41:  8893 
• 5h Minière S. Cintrat J.-C. Synthesis  2001,  705 
• 5i Hemeon I. Singer RD. Chem. Commun.  2002,  1884 
• 5j Naud S. Cintrat J.-C. Synthesis  2003,  1391 
• 6 Murakami M. Amii H. Takizawa N. Ito Y. Organometallics  1993,  12:  4223 
• The palladium/isocyanide complex is also effective for activation of silicon-silicon and silicon-boron bonds, see:
• 7a Ito Y. Suginome M. Murakami M. J. Org. Chem.  1991,  56:  1948 
• 7b Suginome M. Matsuda T. Nakamura H. Ito Y. Tetrahedron  1999,  55:  8787 
• It was formed via disproportionation of silylstannane to distannane followed by bis-stannation of ethyne. For bis-stannation of ethyne see:
• 9a Mitchell TN. Killing AAH. Rutschow D. J. Organomet. Chem.  1983,  241:  C45 
• 9b Mitchell TN. Killing AAH. Rutschow D. J. Organomet. Chem.  1986,  304:  257 
• 11a Taguchi H. Ghoroku K. Tadaki M. Tsubouchi A. Takeda T. J. Org. Chem.  2002,  67:  8450 
• 11b Taguchi H. Tsubouchi A. Takeda T. Tetrahedron Lett.  2003,  44:  5205 
• 12 Pillot J.-P. Dunoguès J. Calas R. Synth. Commun.  1979,  9:  395 
• 13 Tamao K. Nakajo E. Ito Y. Tetrahedron  1988,  44:  3997 
• 14 Liebeskind LS. Fengl RW. J. Org. Chem.  1990,  55:  5359 
• 15 Tamao K. Kobayashi K. Ito Y. Tetrahedron Lett.  1989,  30:  6051 

8

The reaction failed to proceed effectively at room temperature.

10

Interestingly, the reaction with trimethyl(dimethylphenyl-silyl)stannane in place of 1b gave no silastannation product at all. Instead, 1,2-diphenyltetramethyldisilane was formed by disproportionation.