Acylsilane
Acylsilanes are a group of chemical compounds sharing a common functional group with the general structure RC(O)-SiR3.[1]
Synthesis
Acylsilanes can be synthesized by treating acyl anion equivalents with silyl halides (typically
1,3-dithiane, followed by hydrolysis of the dithioacetal group with mercury(II) chloride.[2]
Analogous methods has also been used to produce acylgermanes.
Several approches to acylsilanes start with carboxylic acid derivatives.[1] Esters undergo reductive silylation en route to acylsilanes:
- RCO2Me + 2 tmsCl + Mg → RC(OMe)(Otms)(tms) + MgCl2
- RC(OMe)(Otms(tms) + → RC(O)tms + MeOtms
Tertiary amides react with silyl lithium reagents:
- RCONR'2 + Litms → RC(O)tms + LiNR'2
Acid chlorides are converted using hexamethyldisilane
:
- RCOCl + tms−tms → RC(O)tms + tmsCl
Some acyl silanes are prepared by oxidation of a suitable silanes.[1]
Reactions
Acylsilanes are starting compounds in the Brook rearrangement with vinyl lithium compounds to silyl enol ethers.
Acyl silanes and aryl bromides are
cross coupling reactions:[4]
Further reading
- The reactivity of α- and β-iodo propenoylsilanes: an alternative access to polyunsaturated acylsilanes Alessandro Degl’Innocenti, Antonella Capperucci, Patrizia Scafato, Antonella Telesca Arkivoc 0-005A 2000 Article