Trimethylsilyl trifluoromethanesulfonate

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Trimethylsilyl triflate
)
Trimethylsilyl trifluoromethanesulfonate
Names
Preferred IUPAC name
Trimethylsilyl trifluoromethanesulfonate
Other names
TMSOTf
Trimethylsilyl triflate
TMS triflate
Trifluoromethanesulfonic acid trimethylsilyl ester
Identifiers
3D model (
JSmol
)
ECHA InfoCard
 100.044.136 Edit this at Wikidata
UNII
  • C[Si](C)(C)OS(=O)(=O)C(F)(F)F
Properties
C4H9F3O3SSi
Molar mass 222.25 g·mol−1
Appearance Colorless liquid
Density 1.225 g/mL
Boiling point 140 °C (284 °F; 413 K)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Trimethylsilyl trifluoromethanesulfonate (TMSOTf) is an

trimethylsilyl.[1] It is mainly used to activate ketones and aldehydes in organic synthesis
.

Reactions

TMSOTf is quite sensitive toward hydrolysis:

(CH3)3SiO3SCF3 + H2O → (CH3)3SiOH + HO3SCF3

It is far more electrophilic than trimethylsilyl chloride.

Related to its tendency to hydrolyze, TMSOTf is effective for silylation of alcohols:[2]

(CH3)3SiO3SCF3 + ROH + Et3N → ROSi(CH3)3Si + [Et3NH]O3SCF3

A common use of (CH3)3SiO3SCF3 is for the preparation of silyl enol ethers.[3][4] One example involves the synthesis of the silyl enol ether of camphor:

It was also used in Takahashi Taxol total synthesis and in chemical glycosylation reactions.[5]

Trimethylsilyl trifluoromethanesulfonate has a variety of other specialized uses. It has been use to install tert-alkyl groups on phosphine (R = alkyl):[6]

PH3 + R3C–OAc + Me3SiOTf → [(R3C)2PH2]OTf

Deprotection of

2,6-lutidine.[7][8]

TMSOTf is also a useful reagent to replace metal-halogen bonds with a covalent M-O(SO2CF3) bond, the by-product being the highly volatile TMSCl which is easily removed.

References

  1. ISBN 978-0-471-93623-7
    .
  2. doi:10.15227/orgsyn.092.0309
    .
  3. doi:10.15227/orgsyn.069.0129
    .
  4. doi:10.1055/s-2004-822905
  5. doi:10.15227/orgsyn.081.0225
    .
  6. S2CID 219017552
    .
  7. doi:10.1021/jo9813989
    .
  8. PMID 16435877
    .
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