Allyl silanes are more reactive than vinyl silanes but also react through β-silyl cations
المؤلف:
Jonathan Clayden , Nick Greeves , Stuart Warren
المصدر:
ORGANIC CHEMISTRY
الجزء والصفحة:
ص676
2025-07-05
672
Vinyl silanes have C–Si bonds orthogonal to the p orbitals of the alkene—the C–Si bond is in the nodal plane of the π bond—so there can be no interaction between the C–Si bond and the π bond. Allyl silanes, by contrast, have C–Si bonds that can be, and normally are, parallel to the p orbitals of the π bond so that interaction is possible
Allyl silanes react with electrophiles with even greater regioselectivity than that of vinyl silanes. The cation β to the silyl group is again formed but there are two important differences. Most obviously, the electrophile attacks at the other end of the allylic system and there is no rotation necessary as the C–Si bond is already in a position to overlap efficiently with the intermediate cation. The process is terminated by loss of silicon in the usual way to regenerate an alkene.
Molecular orbitals demonstrate the smooth transition from the allyl silane, which has a π bond and a C–Si σ bond, to the allylic product with a new π bond and a new σ bond to the electrophile. The intermediate cation is mainly stabilized by σ donation from the C–Si bond into the vacant p orbital but it has other σ-donating groups (C–H, C–C, and C–E) that also help. The overall process is electrophilic substitution with allylic rearrangement. Both the site of attachment of the electrophile and the position of the new double bond are dictated by the silicon.
Allyl silanes are rather like silyl enol ethers: they react with electrophiles, provided they are activated, for example by a Lewis acid. Titanium tetrachloride is widely used but other successful Lewis acids include boron trifluoride, aluminium chloride, and trimethylsilyl triflate. Electrophiles include acylium ions produced from acid chlorides, carbocations from tertiary halides or secondary benzylic halides, activated enones, and epoxides all in the presence of Lewis acid. In each case the new bond is highlighted in black.
●β-Silyl cations are important intermediates Vinyl and aryl silanes react with electrophiles at the same (ipso or α) atom occupied by silicon. Allyl silanes react at the end of the alkene furthest from silicon (γ). In both cases a β-silyl cation is an intermediate.
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