Trimethylsilyl trifluoromethanesulfonate

Trimethylsilyl trifluoromethanesulfonate (TMSOTf) is a trifluoromethanesulfonate derivate with a trimethylsilyl R-group. It has similar reactivity to trimethylsilyl chloride, and is also used often in organic synthesis.[1]

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
UNII
  • C[Si](C)(C)OS(=O)(=O)C(F)(F)F
Properties
C4H9F3O3SSi
Molar mass 222.26 g/mol
Appearance colourless 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).
Infobox references

Illustrative reactions

A common application is the conversion of ketones and aldehydes to silyl enol ethers.[2]

The stereoselective synthesis of seven benzylated proanthocyanidin trimers (epicatechin-(4β-8)-epicatechin-(4β-8)-epicatechin trimer (procyanidin C1), catechin-(4α-8)-catechin-(4α-8)-catechin trimer (procyanidin C2), epicatechin-(4β-8)-epicatechin-(4β-8)-catechin trimer and epicatechin-(4β-8)-catechin-(4α-8)-epicatechin trimer derivatives) can be achieved with TMSOTf-catalyzed condensation reaction, in excellent yields. Deprotection of (+)-catechin and (−)-epicatechin trimers derivatives gives four natural procyanidin trimers in good yields.[3]

It has been used in Takahashi Taxol total synthesis or for chemical glycosylation reactions.[4]

Trimethylsilyl trifluoromethanesulfonate is used to install tert-alkyl groups on phosphine (R = alkyl):[5]

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

Deprotection of Boc-protected amines can be achieved using trimethylsilyl trifluoromethanesulfonate and triethylamine or 2,6-lutidine.[6][7]

Trimethylsilyl trifluoromethanesulfonate is a source of trimethylsilyl cation. Other more potent sources silylium cations are known.

See also

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 978-0471936237.{{cite journal}}: CS1 maint: uses authors parameter (link)
  2. Umemoto, Teruo; Tomita, Kyoichi; Kawada, Kosuke (1990). "N-Fluoropyridinium Triflate: An Electrophilic Fluorinating Agent". Organic Syntheses. 69: 129. doi:10.15227/orgsyn.069.0129.
  3. 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
  4. 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.
  5. 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". ACS Catalysis. 10 (10): 5454–5461. doi:10.1021/acscatal.0c01414. ISSN 2155-5435. S2CID 219017552.
  6. 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.
  7. 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.


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