Synfacts 2011(2): 0194-0194  
DOI: 10.1055/s-0030-1259240
Metal-Mediated Synthesis
© Georg Thieme Verlag Stuttgart ˙ New York

3,3-Bissilyl Carbonyl and Enol Derivatives via Brook Rearrangement

Contributor(s): Paul Knochel, Thomas Kunz
Z. Song*, Z. Lei, L. Gao, X. Wu, L. Li
Sichuan University, Chengdu and Lanzhou University, P. R. of China
Further Information

Publication History

Publication Date:
19 January 2011 (online)

Significance

The authors disclose a facile and highly stereoselective retro-[1,4] Brook rearrangement of 3-silyl allyloxysilanes. Basic hydrolysis of the (Z)-3,3-bissilyl lithium enolates leads to 3,3-bissilyl carbonyl compounds, while trapping the enolate with electrophiles provides O-substituted (Z)-3,3-bissilyl enol derivatives. These can undergo a Sakurai reaction with aldehydes affording 1,2-diols diastereoselectively.