Rhodium-Catalyzed Hydroarylation and Hydroalkenylation of Alkynes Using Organo[2-(hydroxymethyl)phenyl]dimethylsilanes

Abstract

The title reaction was found to proceed in the presence of a rhodium/1,2-bis(diphenylphosphino)benzene catalyst. Variously substituted arylethenes and 1,3-dienes were obtained in good yields.

Key words

silicon - alkyne - rhodium - addition reaction

References and Notes

• 1a Hayashi T. Inoue K. Taniguchi N. Ogasawara M. J. Am. Chem. Soc.  2001,  123:  9918 
• 1b Lautens M. Yoshida M. Org. Lett.  2002,  4:  123 
• 1c Murakami M. Igawa H. Helv. Chim. Acta  2002,  85:  4182 
• 1d Lautens M. Yoshida M. J. Org. Chem.  2003,  68:  762 
• 1e Genin E. Michelet V. Genêt J.-P. J. Organomet. Chem.  2004,  689:  3820 
• 1f Genin E. Michelet V. Genêt J.-P. Tetrahedron Lett.  2004,  45:  4157 
• For rhodium-catalyzed arylation of alkynes followed by intra- and intermolecular trap with electrophiles or another unsaturated bond, see:
• 2a Lautens M. Marquardt T. J. Org. Chem.  2004,  69:  4607 
• 2b Shintani R. Okamoto K. Otomaru Y. Ueyama K. Hayashi T. J. Am. Chem. Soc.  2005,  127:  54 
• 2c Miura T. Shimada M. Murakami M. J. Am. Chem. Soc.  2005,  127:  1094 
• 2d Miura T. Sasaki T. Nakazawa H. Murakami M. J. Am. Chem. Soc.  2005,  127:  1390 
• 2e Miura T. Shimada M. Murakami M. Synlett  2005,  667 
• 2f Shintani R. Hayashi T. Org. Lett.  2005,  7:  2071 
• 2g Miura T. Nakazawa H. Murakami M. Chem. Commun.  2005,  2855 
• 2h Shintani R. Tsurusaki A. Okamoto K. Hayashi T. Angew. Chem. Int. Ed.  2005,  44:  3909 
• 2i Matsuda T. Makino M. Murakami M. Angew. Chem. Int. Ed.  2005,  44:  4608 
• 2j Miura T. Murakami M. Org. Lett.  2005,  7:  3339 
• 2k Shintani R. Okamoto K. Hayashi T. Chem. Lett.  2005,  34:  1294 
• 2l Matsuda T. Makino M. Murakami M. Chem. Lett.  2005,  34:  1416 
• 2m Miura T. Shimada M. Murakami M. Angew. Chem. Int. Ed.  2005,  44:  7598 
• 2n Miura T. Shimada M. Murakami M. Chem. Asian J.  2006,  1:  868 
• 2o Miura T. Sasaki T. Harumashi T. Murakami M. J. Am. Chem. Soc.  2006,  128:  2516 
• 2p Kurahashi T. Shinokubo H. Osuka A. Angew. Chem. Int. Ed.  2006,  45:  6336 
• 2q Miura T. Shimada M. Murakami M. Tetrahedron  2007,  63:  6131 
• 2r Shintani R. Takatsu K. Hayashi T. Angew. Chem. Int. Ed.  2007,  46:  3735 
• 2s Miura T. Shimada M. Ku S.-Y. Tamai T. Murakami M. Angew. Chem., Int. Ed.  2007,  46:  7101 
• 2t Miura T. Yamauchi M. Murakami M. Synlett  2007,  2029 
• 2u Miura T. Takanishi Y. Murakami M. Org. Lett.  2007,  9:  5075 
• 2v Harada Y. Nakanishi J. Fujihara H. Tobisu M. Fukumoto Y. Chatani N. J. Am. Chem. Soc.  2007,  129:  5766 
• 2w For a review, see: Miura T. Murakami M. Chem. Commun.  2007,  217 
• For use of organozinc reagents, see:
• 3a Shintani R. Hayashi T. Org. Lett.  2005,  7:  2071 
• 3b Shintani R. Yamagami T. Hayashi T. Org. Lett.  2006,  8:  4799 
• 4a Fujii T. Koike T. Mori A. Osakada K. Synlett  2002,  295 
• 4b For rhodium-catalyzed hydrophosphination of alkynes using silylphosphines, see: Hayashi M. Matsuura Y. Watanabe Y. J. Org. Chem.  2006,  71:  9248 
• For rhodium-catalyzed 1,4-addition reactions using 1, see:
• 5a Nakao Y. Chen J. Imanaka H. Hiyama T. Ichikawa Y. Duan W.-L. Shintani R. Hayashi T. J. Am. Chem. Soc.  2007,  129:  9137 
• 5b Shintani R. Ichikawa Y. Hayashi T. Chen J. Nakao Y. Hiyama T. Org. Lett.  2007,  9:  4643 
• For reviews, see:
• 7a Hiyama T. Kusumoto T. In Comprehensive Organic Synthesis   Vol. 8:  Trost BM. Fleming I. Pergamon; Oxford: 1991.  p.763-792  
• 7b Trost BM. Ball ZT. Synthesis  2005,  853 
• 7c

  For hydrosilylation to synthesize 1, see:

• 7d Nakao Y. Imanaka H. Chen J. Yada A. Hiyama T. J. Organomet. Chem.  2007,  692:  585 
• 8 Peyroux E. Berthiol F. Doucet H. Santelli M. Eur. J. Org. Chem.  2004,  1075 

6

General Experimental Procedure
A solution of [Rh(OH)(cod)]₂ (6.8 mg, 30 µmol Rh) and DPPBz (13.4 mg, 30 µmol) in toluene (1.0 mL) were added 1 (1.50 mmol), 2 (1.00 mmol), and tridecane (an internal standard, 92 mg, 0.50 mmol) sequentially, and the resulting mixture was stirred at 100 °C. After the time specified in Table [1] , the mixture was filtered through a silica gel pad and concentrated in vacuo. The residue was purified by flash chromatography on silica gel to afford the corresponding adducts in yields listed in Table [1] .