Aluminum chloride catalyzed stereo- and regiospecific allylsilylation of alkynes: a convenient route to silyldienes

New Tricks for an Old Dog: Aluminum Compounds as Catalysts in Reduction Chemistry

“…The Jung group also reported on AlCl 3 -catalyzed allylsilylation of unactivated alkenes, diallylsilanes, conjugated dienes, and alkynes with allyltrimethylsilane . In these reactions, the silyl group adds to the external carbon of terminal alkenes and alkynes while the allyl group adds to the inner carbon, in agreement with the silylium ion mechanism.…”

1,5-Hydride Shift in the Aluminum Chloride Promoted Allylsilylation of 5-Silyl-1-alkenes

“…It has been well-known that regiospecific trans -addition and allylic inversion are characteristic of the allylsilylation of alkenes 1-3 and alkynes. , A new carbon−carbon bond formation occurs between the inner carbon of multiple bonds and the terminal carbon of allylsilanes. The bond between the allylic carbon and the silyl group of allylsilanes breaks to afford a new carbon−carbon double bond between the carbons α and β to the silicon of the allylsilanes.…”

“…Recently, we reported the novel aluminum chloride catalyzed addition of allyltrimethylsilane to simple unactivated alkenes, diallylsilanes, conjugated dienes, and alkynes . In the allylsilylation, the silyl group regiospecifically and stereospecifically adds to the terminal carbon and the allyl group to the inner carbon of terminal multiple bonds.…”

Gallium-mediated allyl transfer from bulky homoallyl alcohol to aldehydes or alkynes: Control of dynamic σ-allylgalliums based on retro-allylation reaction

“…The following compounds were characterized according to the literature: 2a [11], 2b [12], 2c [11], 2d [11], 2e [13], 2f [11], 2h [14], 2i [15], 2j [15], 2k-m [11], 2n [16], 2o [14], 2p [17], 2q [17], 6b [18], 6f [18], 6g [18], 6g-d 2 [19], 6g-d 1 [20], 6i [18], and 6n [21]. d 14.34, 15.09, 16.39, 22.89, 29.35, 29.38, 29.40, 29.50, 29.65, 32.10, 32.51, 43.88, 44.83, 76.21, 76.54, 115.86, 116.59, 130.21, 130.63, 133.57.…”