Synthesis of Siloles via Rhodium-Catalyzed Cyclization of Alkynes and Diynes with Hexamethyldisilane

Abstract

A rhodium-catalyzed silylative cyclization of alkynes and 1,6-diynes with hexamethyldisilane is described. These reactions enable the synthesis of densely substituted silole derivatives through the use of a rhodium(I)-norborna-2,5-diene complex as a catalyst.

alkynes - cyclization - diynes - rhodium - siloles

References and Notes

1a Dubac J. Laporterie A. Manuel G. Chem. Rev.  1990,  90:  215 

1b Hissler M. Dyer PW. Réau R. Coord. Chem. Rev.  2003,  244:  1 

1c Yamaguchi S. Tamao K. Chem. Lett.  2005,  34:  2 

2a Yamaguchi S. Tamao K. J. Chem. Soc., Dalton Trans.  1998,  3693 

2b Chen J. Cao Y. Macromol. Rapid Commun.  2007,  28:  1714 

2c Zhan X. Barlow S. Marder SR. Chem. Commun.  2009,  1948 

2d Liu J. Lam JWY. Tang BZ. J. Inorg. Organomet. Polym.  2009,  19:  249 

3a Matsuda T. Kadowaki S. Goya T. Murakami M. Org. Lett.  2007,  9:  133 

3b Matsuda T. Kadowaki S. Murakami M. Chem. Commun.  2007,  2627 

3c Matsuda T. Kadowaki S. Yamaguchi Y. Murakami M. Chem. Commun.  2008,  2744 

3d Matsuda T. Yamaguchi Y. Murakami M. Synlett  2008,  561 

3e Matsuda T. Yamaguchi Y. Murakami M. Synlett  2010,  2743 

4a Ohmura T. Masuda K. Suginome M. J. Am. Chem. Soc.  2008,  130:  1526 

4b Shimizu M. Mochida K. Hiyama T. Angew. Chem. Int. Ed.  2008,  47:  9760 

4c Tobisu M. Onoe M. Kita Y. Chatani N. J. Am. Chem. Soc.  2009,  131:  7506 

4d Ureshino T. Yoshida T. Kuninobu Y. Takai K. J. Am. Chem. Soc.  2010,  132:  14324 

For earlier studies on catalytic construction of silole skeletons, see:

5a Okinoshima H. Yamamoto K. Kumada M. J. Am. Chem. Soc.  1972,  94:  9263 

5b Sakurai H. Kamiyama Y. Nakadaira Y. J. Am. Chem. Soc.  1977,  99:  3879 

5c Seyferth D. Vick SC. Shannon ML. Lim TFO. Duncan DP. J. Organomet. Chem.  1977,  135:  C37 

5d Schäfer A. Weidenbruch M. Pohl S. J. Organomet. Chem.  1985,  282:  305 

5e Ikenaga K. Hiramatsu K. Nasaka N. Matsumoto S. J. Org. Chem.  1993,  58:  5045 

5f Ojima I. Fracchiolla DA. Donovan RJ. Banerji P. J. Org. Chem.  1994,  59:  7594 

5g Palmer WS. Woerpel KA. Organometallics  1997,  16:  1097 

For reviews, see:

6a Han L.-B. Tanaka M. Chem. Commun.  1999,  395 

6b Beletskaya I. Moberg C. Chem. Rev.  2006,  106:  2320 

6c Suginome M. Matsuda T. Ohmura T. Seki A. Murakami M. In Comprehensive Organometallic Chemistry III   Vol. 10:  Crabtree R. Mingos M. Ojima I. Elsevier; Oxford: 2007.  p.725 

7a Walter C. Auer G. Oestreich M. Angew. Chem. Int. Ed.  2006,  45:  5675 

7b Nakao Y. Chen J. Imanaka H. Hiyama T. Ichikawa Y. Duan W.-L. Shintani R. Hayashi T. J. Am. Chem. Soc.  2007,  129:  9137 

7c Walter C. Fröhlich R. Oestreich M. Tetrahedron  2009,  65:  5513 

8a Tobisu M. Kita Y. Chatani N. J. Am. Chem. Soc.  2006,  128:  8152 

8b Tobisu M. Ano Y. Chatani N. Chem. Asian J.  2008,  3:  1585 

8c Tobisu M. Kita Y. Ano Y. Chatani N. J. Am. Chem. Soc.  2008,  130:  15982 

8d Kita Y. Tobisu M. Chatani N. Org. Lett.  2010,  12:  1864 

9

The attempted detection of tetramethylsilane formation was unsuccessful when the reaction was performed in C₆D₆ at 30 ˚C in a sealed NMR tube.

For Si-Me bond cleavage observed in palladium-catalyzed reactions, see:

10a Rauf W. Brown JM. Angew. Chem. Int. Ed.  2008,  47:  4228 

10b Nakao Y. Takeda M. Matsumoto T. Hiyama T. Angew. Chem. Int. Ed.  2010,  49:  4447 

11

The reaction of a diyne with t-BuMe₂SiH catalyzed by a rhodium(I) complex under an ambient pressure of carbon monoxide reportedly gave a silole via a mechanism involving a Si-Me bond cleavage. See ref. 5f.

12

When 1,6-enyne 8 was employed as the substrate, analogous silylative cyclization occurred to afford bicyclic dihydro-silole 9 in 44% isolated yield (Scheme  [4] ).

Scheme 4