Fluoride-induced ß-elimination of silanes having leaving groups in the ß-position 567

are important processes in synthetic chemistry, as, for example, in the removal of
SECTION 5.10
ß-trimethylsilylethoxy groups.
Elimination Reactions

+ – –
RCO2CH2CH2Si(CH3)3 + R4N F RCO2 + CH2 CH2 + FSi(CH3)3

Ref. 312

These reactions proceed by alkoxide or fluoride attack at silicon that results in C−Si
bond cleavage and elimination of the leaving group from the ß-carbon. These reactions
are stereospecific anti eliminations.

Nu:
(CH3)Si3
(CH3)3SiNu + RCH CHR + X–
RCH CHR
X

ß-Elimination reactions of this type can also be effected by converting a ß-hydroxy

group to a better leaving group. For example, conversion of ß-hydroxyalkylsilanes to
the corresponding methanesulfonates leads to rapid elimination.313

CH3SO2Cl
(CH3)3SiCH2CR2 H2C CR2

OH

-Trimethylsilylalkyl trifluoroacetates also undergo facile anti elimination.314

The ability to promote ß-elimination and the electron-donor capacity of the
ß-metalloid substituents can be exploited in a very useful way in synthetic chemistry.315
Vinylstannanes and vinylsilanes react readily with electrophiles. The resulting interme-
diates then undergo elimination of the stannyl or silyl substituent, so that the net effect
is replacement of the stannyl or silyl group by the electrophile. The silyl and stannyl
substituents are crucial to these reactions in two ways. In the electrophilic addition
step, they act as electron-releasing groups that promote addition and control the regio-
chemistry. A silyl or stannyl substituent strongly stabilizes carbocation character at
the ß-carbon atom and thus directs the electrophile to the -carbon.

E
RCH CHMR'3 + E+ RCHCMR3 RCH CHE
+

Computational investigations indicate that there is a ground state interaction

between the alkene  orbital and the carbon-silicon bond that raises the energy of the 

312
P. Sieber, Helv. Chim. Acta, 60, 2711 (1977).
313
F. A. Carey and J. R. Toler, J. Org. Chem., 41, 1966 (1976).
314
M. F. Connil, B. Jousseaune, N. Noiret, and A. Saux, J. Org. Chem., 59, 1925 (1994).
315
T. H. Chan and I. Fleming, Synthesis, 761 (1979); I. Fleming, Chem. Soc. Rev., 10, 83 (1981).