A Mild and Efficient Desilylation of O-tert-Butyldimethylsilyl Ethers Mediated by Chlorotrimethylsilane and Potassium Fluoride Dihydrate in Acetonitrile

Abstract

Desilylation of O-tert-butyldimethylsilyl ethers was achieved by a reagent system consisting of chlorotrimethylsilane and potassium fluoride dihydrate in acetonitrile. This alternative desilylation procedure is chemoselective, generally effective and operationally simple, and should find practical applications in ­organic synthesis.

Key words

desilylation - potassium fluoride - chlorotrimethyl­silane - O-tert-butyldimethylsilyl ether

References and Notes

• 1 Corey EJ. Venkateswarlu A. J. Am. Chem. Soc.  1972,  94:  6190 
• 2a Greene TW. Wuts PGM. Protective Groups in Organic Synthesis   2rd ed.:  John Wiley and Sons; New York: 1991.  p.77-84  
• 2b Greene TW. Wuts PGM. Protective Groups in Organic Synthesis   2nd ed.:  John Wiley and Sons; New York: 1991.  p.414-416  
• 2c Kocienski PJ. Protecting Groups   Georg Thieme Verlag; New York: 1994.  p.185-237  
• 2d Jarowicki K. Kocienski P. J. Chem. Soc., Perkin Trans. 1  1999,  1589 
• 3a Farras J. Serra C. Vilarrasa J. Tetrahedron Lett.  1998,  39:  327 
• 3b Bartoli G. Bosco M. Marcantoni E. Sambri L. Torregiani E. Synlett  1998,  209 
• 3c Lipshutz BH. Keith J. Tetrahedron Lett.  1998,  39:  2495 
• 3d Oriyama T. Kobayashi Y. Noda K. Synlett  1998,  1047 
• 3e Quici S. Cavazzini M. Ceragioli S. Montanari F. Pozzi G. Tetrahedron Lett.  1999,  40:  3647 
• 3f Ranu BC. Jana U. Majee A. Tetrahedron Lett.  1999,  40:  1985 
• 3g Crouch RD. Stieff M. Frie J. Cadwallader AB. Bevis DC. Tetrahedron Lett.  1999,  40:  3133 
• 3h Hunter R. Hinz W. Richards P. Tetrahedron Lett.  1999,  40:  3643 
• 3i Sabitha G. Syamala M. Yadav JS. Org. Lett.  1999,  1:  1701 
• 3j Paterson I. Cowden CJ. Rahn VS. Woodrow MD. Synlett  1998,  915 
• 3k Kartha KPR. Field RA. Synlett  1999,  311 
• 3l Ramasamy KS. Averett D. Synlett  1999,  709 
• 3m Yu Z. Verkade JG. J. Org. Chem.  2000,  65:  2065 
• 3n Bajwa JS. Vivelo J. Slade J. Repic O. Blacklock T. Tetrahedron Lett.  2000,  41:  6021 
• 3o Gopinath R. Patel BK. Org. Lett.  2000,  2:  4177 
• 3p Wang M. Li C. Yin D. Liang X.-T. Tetrahedron Lett.  2002,  43:  8727 
• 3q Wu Y. Huang J.-H. Shen X. Hu Q. Tang C.-J. Li L. Org. Lett.  2002,  4:  2141 
• 3r Barros MT. Maycock CD. Thomassigny C. Synlett  2001,  1146 
• 3s Jeong YJ. Lee JH. Park ES. Yoon CM. J. Chem. Soc., Perkin Trans. 1  2002,  1223 
• 3t Oyama K.-I. Kondo T. Org. Lett.  2003,  5:  209 
• 4a Sinhababu AK. Kawase M. Borchardt RT. Tetrahedron Lett.  1987,  28:  4139 
• 4b Sinhababu AK. Kawase M. Borchardt RT. Synthesis  1988,  710 
• 4c Schmittling EA. Sawyer JS. Tetrahedron Lett.  1991,  32:  7207 
• 5 Carpino LA. Sau AC. J. Chem. Soc., Chem. Commun.  1979,  514 
• 6 Maiti G. Roy SC. Tetrahedron Lett.  1997,  38:  495 ; see also ref. 3a,b,d,o
• Detected by GCMS analysis of the crude products. For halogenation of alcohols by TMSCl and metal halide salts, see:
• 7a Olah GA. Narang SC. Balaram-Gupta BG. Malhotra R. J. Org. Chem.  1979,  44:  1247 
• 7b Olah GA. Balaram-Gupta BG. Malhotra R. Narang SC. J. Org. Chem.  1980,  45:  1638 
• 8 Shimano M. Shibata T. Kamei N. Tetrahedron Lett.  1998,  39:  4363 
• 9a Chuit C. Corriu RJP. Reye C. Young JC. Chem. Rev.  1993,  93:  1371 
• 9b Bassindale AR. Stout T. Tetrahedron Lett.  1985,  26:  3403 
• For a review, see:
• 10a Dilman AD. Loffe S. Chem. Rev.  2003,  103:  733 
• For TMSCl-mediated addition reactions, see:
• 10b Frantz DE. Singleton DA. J. Am. Chem. Soc.  2000,  122:  3288 ; and references therein
• 10c Corey EJ. Li W. Nagamitsu T. Angew. Chem. Int. Ed.  1998,  37:  1676