Tris(trimethylsilyl)silane (TTMSS)

Introduction

Tris(trimethylsilyl)silane (TTMSS) has been used in many transformations, especially in radical chain reactions. Chatgilialoglu et al. demonstrated that this reagent can be a valuable substitute for tin reagents commonly used in radical processes. [1] The Si-H bond dissociation ­energy in TTMSS of 79 kcal·mol^-1 is very similar to the Sn-H bond dissociation energy of 74 kcal·mol^-1 in Bu₃SnH. [2] The ease of purification and the low toxicity of TTMSS make it an attractive alternative to tin as a ­reducing agent. Interestingly, there are also reports ­demonstrating that the behavior of TTMSS can be very different from that of tin hydrides. [3]

This reagent is commercially available as a colorless ­liquid. [4] It should be stored under nitrogen because it is sensitive towards oxygen. [5] Reactions such as functional reductions, [6] hydrosilylations, [7] intramolecular cyclizations, [8] intermolecular reactions, [9] and non-radical reactions [10] can be performed with TTMSS.

References

• 1a Chatgilialoglu C. Organosilanes in Radical Chemistry: Principles, Methods and Applications   John Wiley & Sons; Chichester: 2004.  p.49-227 
• 1b Chatgilialoglu C. In Radicals in Organic Synthesis   Vol. 1:  Renaud P. Sibi MP. Wiley-VCH; Weinheim: 2001.  p.28-49  
• 2 Kanabus-Kaminska JM. Hawari JA. Griller D. Chatgilialoglu C. J. Am. Chem. Soc.  1987,  109:  5267 
• 3a Some examples: Curran DP. Keller AI. J. Am. Chem. Soc.  2006,  128:  13706 
• 3b Yamaguchi K. Kazuta Y. Abe H. Matsuda A. Shuto S. J. Org. Chem.  2003,  68:  9255 
• 3c Lee E. Park CM. Yun JS. J. Am. Chem. Soc.  1995,  117:  8017 
• 3d Apeloig Y. Nakash M. J. Am. Chem. Soc.  1994,  116:  10781 
• 4 Procedure for the preparation of TTMSS: Dickhaut J. Giese B. Org. Synth.  1991,  70:  164 
• 5 Chatgilialoglu C. Guarini A. Guerrini A. Seconi G. J. Org. Chem.  1992,  57:  2207 
• 6 Giese B. Damm W. Dickhaut J. Wetterich F. Sun S. Curran DP. Tetrahedron Lett.  1991,  32:  6097 
• 7 Kopping B. Chatgilialoglu C. Zenhder M. Giese B. J. Org. Chem.  1992,  57:  3994 
• 8 Usui S. Paquette LA. Tetrahedron Lett.  1999,  40:  3495 
• 9 Schneider H. Fiander H. Harisson KA. Watson M. Burton GW. Arya P. Bioorg. Med. Chem. Lett.  1996,  6:  637 
• 10 Watanabe H. Araki KI. Matsumoto H. Nagai Y. J. Organomet. Chem.  1974,  69:  389 
• 11 Gandon LA. Russell AG. Guveli T. Brodwolf AE. Kariuki BM. Spencer N. Snaith JS. J. Org. Chem.  2006,  71:  5198 
• 12 Liu Y. Yamazaki S. Yamabe S. J. Org. Chem.  2005,  70:  556 
• 13 Braslau R. Tsimelzon A. Gewandter J. Org. Lett.  2004,  6:  2233 
• 14 Maulide A. Markov IE. Chem. Commun.  2006,  1200 
• 15 Lopin C. Gouhier G. Gautier A. Piettre SR. J. Org. Chem.  2003,  68:  9916 
• 16 Tojino M. Noboru O. Fukuyama T. Matsubara H. Schiesser CH. Kuriyama H. Miyazato H. Minakata S. Komatsu M. Ryu I. Org. Biomol. Chem.  2003,  1:  4262 
• 17 Oba M. Suyama M. Shimamura A. Nishiyama K. Tetrahedron Lett.  2003,  44:  4027 
• 18 Dang HS. Roberts BP. J. Chem. Soc., Perkin Trans. 1  1996,  769