Trimethylsilyl trifluoromethanesulfonate

Names
Preferred IUPAC name

Trimethylsilyl trifluoromethanesulfonate

Other names

TMSOTf
Trimethylsilyl triflate
TMS triflate
Trifluoromethanesulfonic acid trimethylsilyl ester

Identifiers

CAS Number

* 27607-77-8 Y

3D model (JSmol)

* Interactive image

ChemSpider |

* 58839

EC Number |

* 248-565-4

PubChem CID

* 65367

UNII |

* Z84V0CBH9J Y

InChI

* InChI=1S/C4H9F3O3SSi/c1-12(2,3)10-11(8,9)4(5,6)7/h1-3H3

Key: FTVLMFQEYACZNP-UHFFFAOYSA-N

SMILES

* C[Si](C)(C)OS(=O)(=O)C(F)(F)F

Properties

Chemical formula

| C4H9F3O3SSi
Molar mass | 222.25 g·mol−1
Appearance  | Colorless liquid
Density | 1.225 g/mL
Boiling point |  140 °C (284 °F; 413 K)
Hazards
GHS pictograms |
GHS Signal word | Danger

GHS hazard statements

| H226, H314

GHS precautionary statements

| P210, P233, P240, P241, P242, P243, P260, P264, P280, P301+330+331, P302+361+354Script error: No such module "Preview warning".Category:GHS errors, P303+361+353, P304+340, P305+354+338Script error: No such module "Preview warning".Category:GHS errors, P316Script error: No such module "Preview warning".Category:GHS errors, P321, P363, P370+378, P403+235, P405, P501

Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Infobox references

Tracking categories (test):

* SizeSet

Trimethylsilyl trifluoromethanesulfonate (TMSOTf) is an organosilicon compound with the formula (CH

3SiO
3SCF
3. It is a colorless moisture-sensitive liquid. It is the trifluoromethanesulfonate derivative of trimethylsilyl.[1] It is mainly used to activate ketones and aldehydes in organic synthesis.

## Reactions

TMSOTf is quite sensitive toward hydrolysis:

(CH

3SiO
3SCF
3 \+ H
2O → (CH

3SiOH + HO
3SCF

It is far more electrophilic than trimethylsilyl chloride.

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

(CH

3SiO
3SCF
3 \+ ROH + Et
3N → ROSi(CH

3Si + [Et
3NH]O
3SCF

A common use of (CH

3SiO
3SCF
3 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 used to install tert-alkyl groups on phosphine (R = alkyl):[6]

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

Deprotection of Boc-protected amines can be achieved using trimethylsilyl trifluoromethanesulfonate and triethylamine or 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. ↑ Joseph Sweeney; Gemma Perkins; Enrique Aguilar; Manuel A. Fernández-Rodríguez; Rodolfo Marquez; Eric Amigues; Ricardo Lopez-Gonzalez (2018). "Trimethylsilyl Trifluoromethanesulfonate". Encyclopedia of Reagents for Organic Synthesis. doi:10.1002/047084289X.rt338. ISBN 978-0-471-93623-7.
2. ↑ Boeckman, Robert; Tusch, Douglas J.; Biegasiewicz, Kyle F. (2015). "(S)-1,1-Diphenylprolinol Trimethylsilyl Ether". Organic Syntheses 92: 309–319. doi:10.15227/orgsyn.092.0309.
3. ↑ Umemoto, Teruo; Tomita, Kyoichi; Kawada, Kosuke (1990). "N-Fluoropyridinium Triflate: An Electrophilic Fluorinating Agent". Organic Syntheses 69: 129. doi:10.15227/orgsyn.069.0129.
4. ↑ Efficient Stereoselective Synthesis of Proanthocyanidin Trimers with TMSOTf-Catalyzed Intermolecular Condensation. Akiko Saito, Akira Tanaka, Makoto Ubukata and Noriyuki Nakajima, Synlett, 2004, volume 6, pages 1069-1073, doi:10.1055/s-2004-822905
5. ↑ Love, Kerry R.; Seeberger, Peter H. (2005). "Synthesis and Use of Glycosyl Phosphates as Glycosyl Donors". Organic Syntheses 81: 225. doi:10.15227/orgsyn.081.0225.
6. ↑ Barber, Thomas; Argent, Stephen P.; Ball, Liam T. (2020-05-15). "Expanding Ligand Space: Preparation, Characterization, and Synthetic Applications of Air-Stable, Odorless Di- tert -alkylphosphine Surrogates" (in en). ACS Catalysis 10 (10): 5454–5461. doi:10.1021/acscatal.0c01414. ISSN 2155-5435. https://pubs.acs.org/doi/10.1021/acscatal.0c01414.
7. ↑ Kuehne, Martin E.; Xu, Feng (1 December 1998). "Syntheses of Strychnan- and Aspidospermatan-Type Alkaloids. 10. An Enantioselective Synthesis of (−)-Strychnine through the Wieland−Gumlich Aldehyde". The Journal of Organic Chemistry 63 (25): 9427–9433. doi:10.1021/jo9813989.
8. ↑ Doi, Takayuki; Numajiri, Yoshitaka; Munakata, Asami; Takahashi, Takashi (1 February 2006). "Total Synthesis of Apratoxin A". Organic Letters 8 (3): 531–534. doi:10.1021/ol052907d. PMID 16435877.

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*[CID]: Compound ID
*[H226]: Flammable liquid and vapour
*[H314]: Causes severe skin burns and eye damage
*[P210]: Keep away from heat/sparks/open flames/hot surfaces – No smoking
*[P233]: Keep container tightly closed
*[P240]: Ground/bond container and receiving equipment
*[P241]: Use explosion-proof electrical/ventilating/light/…/equipment
*[P242]: Use only non-sparking tools
*[P243]: Take precautionary measures against static discharge
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*[P264]: Wash … thoroughly after handling
*[P280]: Wear protective gloves/protective clothing/eye protection/face protection
*[P301+330+331]: IF SWALLOWED: Rinse mouth. Do NOT induce vomiting
*[P303+361+353]: IF ON SKIN (or hair): Remove/Take off immediately all contaminated clothing. Rinse skin with water/shower
*[P304+340]: IF INHALED: Remove victim to fresh air and keep at rest in a position comfortable for breathing
*[P321]: Specific treatment (see … on this label)
*[P363]: Wash contaminated clothing before reuse
*[P370+378]: In case of fire: Use … for extinction
*[P403+235]: Store in a well ventilated place. Keep cool
*[P405]: Store locked up
*[P501]: Dispose of contents/container to …