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Bis(trimethylsilyl)acetylene

Bis(trimethylsilyl)acetylene (BTMSA) is an organosilicon compound with the formula Me<sub>3</sub>SiC≡CSiMe<sub>3</sub> (Me = methyl). It is a crystalline solid that melts slightly above room temperature and is soluble in organic solvents. This compound is used as a surrogate for acetylene.

BTMSA is prepared by treating acetylene with butyllithium followed by addition of trimethylsilyl chloride (Me = CH<sub>3</sub>, Bu = C<sub>4</sub>H<sub>9</sub>):

HC≡CH + 2 BuLi → LiC≡CLi + 2 BuH
LiC≡CLi + 2 Me<sub>3</sub>SiCl → Me<sub>3</sub>SiC≡CSiMe<sub>3</sub> + 2 LiCl

An alternative source is the reaction of dimethyl acetylenedicarboxylate and 3,4-bis(trimethylsilyl)furan.

Reactions

BTMSA is used as a nucleophile in Friedel-Crafts type acylations and alkylations and a precursor to lithium trimethylsilylacetylide. The TMS groups can be removed with tetra-n-butylammonium fluoride (TBAF) and replaced with protons. BTMSA is also a useful reagent in cycloaddition reactions. Illustrating its versatility, BTMSA was used in a concise total synthesis of (±)-estrone. A key step in this synthesis was the formation of the steroidal skeleton, catalyzed by CpCo(CO)<sub>2</sub>.

BTMSA also serves as a ligand in organometallic chemistry. For example, it forms stable adducts with metallocenes.

Cp<sub>2</sub>TiCl<sub>2</sub> + Mg + Me<sub>3</sub>SiC≡CSiMe<sub>3</sub> → Cp<sub>2</sub>Ti(η²-Me<sub>3</sub>SiC₂SiMe<sub>3</sub>) + MgCl<sub>2</sub>

References