Acylsilane Explained

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 trimethylsilyl chloride, tmsCl). Silylation of 2-lithio-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:

Tertiary amides react with silyl lithium reagents:

Acid chlorides are converted using hexamethyldisilane:

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 coupling partners in Pd-catalyzed cross coupling reactions:^[3]

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

Notes and References

1. 10.1039/c3cs60185d . Acylsilanes: Valuable Organosilicon Reagents in Organic Synthesis . 2013 . Zhang . Hui-Jun . Priebbenow . Daniel L. . Bolm . Carsten . Chemical Society Reviews . 42 . 21 . 8540–8571 . 23942548 .
2. Brook. A. G.. Jan 1, 1967. Synthesis of Silyl and Germyl Ketones. Journal of the American Chemical Society. 89. 2. 431–434. 10.1021/ja00978a047.
3. 10.15227/orgsyn.098.0068 . Palladium-Catalyzed Acetylation of Arylbromides . 2021 . Mehta . Milauni M. . Andrew V. . Kelleghan. Neil K.. Garg. Organic Syntheses . 98 . 68–83 .