Brønsted Acid Catalyzed 1,2-Silyl Shift in Propargyl Silanes: Synthesis of Silyl Dienes and Silyl Indenes

Journal of Organic Chemistry 2019
Mikus Puriņš, Anatolijs Mišņovs, Māris Turks

A general method for generation of allyl carbenium ions from propargyl silanes via a 1,2-silyl shift by Brønsted acids is reported. Two possible reaction pathways are described. Deprotonation results in silyl dienes with yields from 52% to 92%. Intramolecular Friedel-Crafts reactions of aryl-substituted systems give access to silyl indenes with yields of 18-90% depending on the substitution pattern. The obtained products have been shown to react as alkenyl silanes in Hiyama coupling and electrophilic substitution and as dienes in Diels-Alder cycloaddition.

DOI
10.1021/acs.joc.8b02735
Hyperlink
https://pubs.acs.org/doi/10.1021/acs.joc.8b02735

Puriņš, M., Mišņovs, A., Turks, M. Brønsted Acid Catalyzed 1,2-Silyl Shift in Propargyl Silanes: Synthesis of Silyl Dienes and Silyl Indenes. Journal of Organic Chemistry, 2019, Vol. 84, No. 6, pp.3595-3611. ISSN 0022-3263. Available from: doi:10.1021/acs.joc.8b02735

Publication language
English (en)