1,3-Difunctionalization of Propargyl Silanes with Concomitant 1,2-Silyl Shift: Synthesis of Allyl Functionalized Vinyl Silanes

Organic Letters 2023
Rūdolfs Beļaunieks, Mikus Puriņš, Rebeka Anna Līpiņa, Anatolijs Mišņovs, Māris Turks

Terminal alkynes with a silyl group at the propargylic position upon activation with electrophiles such as N-bromosuccinimide undergo (E)-selective 1,2-silyl group migration. Subsequently, an allyl cation is formed that is intercepted by an external nucleophile. This approach provides allyl ethers and esters with stereochemically defined vinyl halide and silane handles for further functionalization. The scope of propargyl silanes and electrophile-nucleophile pairs are investigated, and various trisubstituted olefins are prepared in up to 78% yield. The obtained products have been demonstrated to serve as building blocks for transition-metal-catalyzed cross-couplings of vinyl halides, silicon-halogen exchange, and allyl acetate functionalization reactions.

Keywords
Allyl group, Functionalization, Group 14 compounds, Inorganic compounds, Propargyls
DOI
10.1021/acs.orglett.3c01245
Hyperlink
https://pubs.acs.org/doi/10.1021/acs.orglett.3c01245

Beļaunieks, R., Puriņš, M., Līpiņa, R., Mišņovs, A., Turks, M. 1,3-Difunctionalization of Propargyl Silanes with Concomitant 1,2-Silyl Shift: Synthesis of Allyl Functionalized Vinyl Silanes. Organic Letters, 2023, Vol. 25, No. 25, pp.4627-4631. ISSN 1523-7060. e-ISSN 1523-7052. Available from: doi:10.1021/acs.orglett.3c01245

Publication language
English (en)