Copper(I) tert-Butoxide-Promoted Allylation of β-Triphenylsilyl Allylic Alcohols­ via 1,3 C ^sp² -to-O Silyl Migration

Abstract

The substitution of the silyl group in vinylsilanes by an allylic group proceeded when β-triphenylsilylallyl alcohols were treated with copper(I) tert-butoxide and allylic halides. This reaction is the first synthetic application of 1,3 C^sp2-to-O silyl migration which provides a useful method for generation of vinyl anion equivalents.

allylations - allylic alcohols - copper alkoxides - silyl rearrangemen­t - silyl ethers

References

1a Brook AG. Pure Appl. Chem.  1966,  13:  215 

1b Brook AG. Acc. Chem. Res.  1974,  7:  77 

1c Moser WH. Tetrahedron  2001,  57:  2065 

1d Kira M. Iwamoto T. In The Chemistry of Organosilicon Compounds   Vol. 3:  Rappoport Z. Apeloig Y. Wiley; Chichester: 2001.  p.853 

2a For 1,4 C^sp2-to-O silyl migration, see: Spinazzé PG. Keay BA. Tetrahedron Lett.  1989,  30:  1765 

2b See also: Kim KD. Magriotis PA. Tetrahedron Lett.  1990,  31:  6137 

2c See also: Lautens M. Delanghe PHM. Goh JB. Zhang CH. J. Org. Chem.  1995,  60:  4213 

2d See also: Bures E. Spinazzé PG. Beese G. Hunt IR. Rogers C. Keay BA. J. Org. Chem.  1997,  62:  8741 

2e See also: Moser WH. Endsley KE. Colyer JT. Org. Lett.  2000,  2:  717 

2f See also: Moser WH. Zhang J. Lecher CS. Frazier TL. Pink M. Org. Lett.  2002,  4:  1981 

2g For 1,3 C^sp2-to-O silyl migration, see: Wilson SR. Georgiadis GM. J. Org. Chem.  1983,  48:  4143 

2h See also: Sato F. Tanaka Y. Sato M. J. Chem. Soc., Chem. Commun.  1983,  165 

2i See also: Urabe H. Sato F. J. Am. Chem. Soc.  1999,  121:  1245 

2j See also: Radinov R. Schnurman ES. Tetrahedron Lett.  1999,  40:  243 

3a Taguchi H. Ghoroku K. Tadaki M. Tsubouchi A. Takeda T. Org. Lett.  2001,  3:  3811 

3b Taguchi H. Ghoroku K. Tadaki M. Tsubouchi A. Takeda T. J. Org. Chem.  2002,  67:  8450 

3c Taguchi H. Miyashita H. Tsubouchi A. Takeda T. Chem. Commun.  2002,  2218 

3d Taguchi H. Tsubouchi A. Takeda T. Tetrahedron Lett.  2003,  44:  5205 

3e Taguchi H. Takami K. Tsubouchi A. Takeda T. Tetrahedron Lett.  2004,  45:  429 

4 Dawson IM. Gregory JA. Herbert RB. Sammens PG. J. Chem. Soc., Perkin Trans. 1  1988,  2585 

5 Chan TH. Mychajlowskij W. Ong BS. Harpp DN. J. Org. Chem.  1978,  43:  1526 

6 Tsuda T. Hashimoto T. Saegusa T. J. Am. Chem. Soc.  1972,  94:  658 

7a Hudrlik PF. Hudrlik AM. Kulkarni AK. J. Am. Chem. Soc.  1982,  104:  6809 

7b Kawashima T. J. Organomet. Chem.  2000,  661:  256 ; and references therein

8 For a similar reactivity order of the silyl migration, see: Takaku K. Shinokubo H. Oshima K. Tetrahedron Lett.  1998,  39:  2575