Studies on hydrozirconation of 1-alkynyl sulfoxides or sulfones and the application for the synthesis of stereodefined vinyl sulfoxides or sulfones.

Department of Chemistry, Zhejiang University (Campus Xixi), Hangzhou 310028, Zhejiang, P. R. China.
The Journal of Organic Chemistry (Impact Factor: 4.56). 04/2003; 68(5):1958-63. DOI: 10.1021/jo0111154
Source: PubMed

ABSTRACT The hydrozirconation reaction of 1-alkynyl sulfoxides or sulfones with Cp2Zr(H)Cl in THF at room temperature predominantly gave Z-beta-zirconated vinyl sulfoxides or sulfones with excellent regioselectivity. Compared with 1-alkynyl sulfoxides, the hydrozirconation reaction of 1-alkynyl sulfones exhibits great synthetic potential, leading to the efficient preparation of Z-beta-halovinyl sulfones, Z-beta-sulfonyl alpha,beta-unsaturated ketones, and Z-beta-alkynyl vinyl sulfones. Although the reaction mechanisms are still not clear, the neighboring group participation of the sulfinyl or sulfonyl group may be playing an important role in this unique hydrozirconation reaction.