27607-77-8 Usage
Description
Trimethylsilyl trifluoromethanesulfonate, also known as TMSOTf, is a trialkylsilyl triflate used as a catalyst and silylating agent in organic synthesis. It is a clear colorless to light brown fuming liquid with a boiling point of 45-47 °C/17 mmHg and a density of 1.225 g/cm3.
Uses
1. Silylation:
Trimethylsilyl trifluoromethanesulfonate is used as a catalyst for the conversion of carbonyl compounds to their enol ethers, which is significantly faster with TMSOTf/triethylamine than with chlorotrimethylsilane. It is also used in the conversion of dicarbonyl compounds to bis-enol ethers and has a tendency towards C-silylation, especially in the reaction of esters.
2. Carbonyl Activation:
Used in the chemical industry, TMSOTf facilitates 1,3-dioxolanation of conjugated enals in the presence of 1,2-bis(trimethylsiloxy)ethane, allowing for highly selective protection of sterically differentiated ketones. It also mediates a stereoselective aldol-type condensation of silyl enol ethers and acetals (or orthoesters) with aldehydes, and induces stereoselective cyclization of α,β-unsaturated enamide esters.
3. Conjugate Addition:
In the field of organic chemistry, TMSOTf greatly facilitates the conjugate addition of alkynyl organometallic reagents to enones, particularly with alkynyl zinc reagents that are normally unreactive with α,β-unsaturated carbonyl compounds.
4. Nitrone Formation:
Trimethylsilyl trifluoromethanesulfonate is used as a catalyst to accelerate the formation of nitrones by reacting aldehydes and ketones with N-methyl-N,O-bis(trimethylsilyl)hydroxylamine, especially when the carbonyl group is under a strong electronic influence.
5. Carbohydrate Synthesis:
Used in the carbohydrate industry, TMSOTf catalyzes the allylation of methyl glucopyranosides and glycopyranosyl chlorides with allylsilanes, predominantly yielding α-allylated carbohydrate analogs. It also activates many selective glycosidation reactions, which are of massive importance and widespread employment in the synthesis of complex carbohydrates.
6. O-, C-, and N-Silylation:
Trimethylsilyl trifluoromethanesulfonate is used as a catalyst for the formation of TMS ethers through the reaction of alcohols with TMSOTf and an amine in dichloromethane. It also facilitates C-silylation of secondary amides and N-silylation of α-amino acids, with the latter being effective for glycine and N-mono-silylation for other α-amino acids due to steric hindrance.
7. C,O-Bis-silylation:
In the field of organic synthesis, TMSOTf enables the bis-silylation of α,β-unsaturated carbonyl compounds through palladium-TMSOTf-catalyzed addition of disilanes to enones, enals, or aromatic aldehydes via an η3-silyloxyallylpalladium intermediate.
8. Acetal and Nitrone Activation:
Trimethylsilyl trifluoromethanesulfonate acts as a catalyst for the addition of various nucleophiles to N,O-acetals and the nucleophilic addition to aldonitrones, depending on the nature of the metal involved and the presence/absence of an activator.
9. Epoxide Ring Opening:
Used in organic synthesis, TMSOTf catalyzes one-pot alkylation-O-silylation reactions of epoxides, yielding excellent results.
10. Cleavage of Protecting Groups:
In the field of organic chemistry, TMSOTf is used to conveniently deprotect THP ethers of primary, secondary, and phenolic alcohols at room temperature.
11. Hypervalent Iodine Chemistry:
Trimethylsilyl trifluoromethanesulfonate promotes the formation of hypervalent iodine complexes in organic synthesis.
12. Lewis Acid Preparation:
Used in the chemical industry, TMSOTf is combined with boron trifluoride ethyl ether to prepare a more powerful Lewis acid, especially effective in acetonitrile solvent. This combination is also used in Dieckmann-like cyclization of ester-imides and diesters.
Check Digit Verification of cas no
The CAS Registry Mumber 27607-77-8 includes 8 digits separated into 3 groups by hyphens. The first part of the number,starting from the left, has 5 digits, 2,7,6,0 and 7 respectively; the second part has 2 digits, 7 and 7 respectively.
Calculate Digit Verification of CAS Registry Number 27607-77:
(7*2)+(6*7)+(5*6)+(4*0)+(3*7)+(2*7)+(1*7)=128
128 % 10 = 8
So 27607-77-8 is a valid CAS Registry Number.
InChI:InChI=1/C18H3F35O6/c19-2(1-54,8(26,27)28)55-15(46,47)4(22,10(32,33)34)57-17(50,51)6(24,12(38,39)40)59-18(52,53)7(25,13(41,42)43)58-16(48,49)5(23,11(35,36)37)56-14(44,45)3(20,21)9(29,30)31/h54H,1H2
27607-77-8Relevant articles and documents
NEW METHOD FOR THE PREPARATION OF t-BUTYLDIMETHYLSILYL TRIFLATE
Hudrlik, Paul F.,Kulkarni, Ashok K.
, p. 1389 - 1390 (1985)
t-Butyldimethylsilyl triflate is easily prepared from the reaction of triflic acid with isopropenyltrimethylsilane.
ELECTROPHILE-INITIATED SELECTIVE RING TRANSFORMATIONS OF CYCLOPROPYL KETONES
Demuth, Martin,Mikhail, Gamal
, p. 991 - 997 (1983)
Electrophile-mediated cyclopropane cleavage in tricyclo2,8>octan-3-one (1a) is increasingly directed towards the maximum bond overlap site in the following order of reagents: acetyl methanesulfonate, +Br(1-) or I(1-); t-butyl-dimethylsilyl iodide; t-butyldimethylsilyl trifluoroacetate; trimethylsilyl trifluoroacetate.The latter reagent gives rise to one single regioisomer (->6a).Routine yields of isolated products lie between 78 and 87percent.Increasing regioselectivity is governed by increasing electrophilic power and lowered nucleophilic strength of the reagents.Independent of these two factors, a C(4)-exo substituent in 1 directs the opening modes undirectionally (->2b, 6b).Irrespective of the substitution pattern at C(4) (1a-d), the cyclopropane moiety rearranges smoothly to olefinic ketones (8a-d) when the polymer-supported triflate analog Nafion-TMS is used in toluene at 80 deg C.The reaction proceeds via intramolecular proton (deuterion) abstraction by the transient electron-rich enoxy double bond.This is the first fully proved case of such an intramolecular process.Aro-semibullvalenes (18,22) similarly rearrange to aro-semibarrelenes (e.g. 21, 23) in the presence of Nafion-TMS.The latter rearrangement also takes place at room temperature when 18 or 22 are treated with commercial tetramethylsilane (TMS) and a catalytic amount of trifluoroacetic acid.An unknown impurity in the TMS reacts with the acid to form a powerful electrophilic composition.A cheap and convenient in situ preparation of TMS-triflate is described by mixing trifluoromethanesulfonic acid and TMS at room temperature.
A Convenient in situ Preparation of Trimethylsilyl Trifluoromethanesulfonate
Demuth, Martin,Mikhail, Gamal
, p. 827 (1982)
-
A New, Simple in Situ Preparation of Trimethylsilyl Trifluoromethanesulfonate
Ballester, Montserrat,Palomo, Antonio Luis
, p. 571 - 572 (1983)
-
Divergent Synthesis of Vinyl-, Benzyl-, and Borylsilanes: Aryl to Alkyl 1,5-Palladium Migration/Coupling Sequences
Han, Jie-Lian,Ju, Cheng-Wei,Qin, Ying,Zhao, Dongbing
supporting information, p. 6555 - 6560 (2020/03/03)
Organosilicon compounds have been extensively utilized both in industry and academia. Studies on the syntheses of diverse organosilanes is highly appealing. Through-space metal/hydrogen shifts allow functionalization of C?H bonds at a remote site, which are otherwise difficult to achieve. However, until now, an aryl to alkyl 1,5-palladium migration process seems to have not been presented. Reported herein is the remote olefination, arylation, and borylation of a methyl group on silicon to access diverse vinyl-, benzyl-, and borylsilanes, constituting a unique C(sp3)?H transformation based on a 1,5-palladium migration process.
Redox Reactions of a Stable Dialkylphosphinyl Radical
Hirakawa, Fumiya,Ichikawa, Hitomi,Ishida, Shintaro,Iwamoto, Takeaki
supporting information, p. 2714 - 2716 (2015/06/30)
A stable dialkylphosphinyl radical, 2,2,5,5-tatrakis(trimethylsilyl)-1-phosphacyclopentan-1-yl (RH2P?), showed both irreversible one-electron oxidation and reduction peaks at -0.24 and -2.29 V vs ferrocene/ferrocenium couple. One-electron reduction of RH2P? with KC8 in the presence of 18-crown-6 (18-c-6) or [2.2.2]cryptand (crypt-222) gave the corresponding phosphides [K(18-c-6)]+[RH2P]- and [K(crypt-222)]+[RH2P]-. Whereas [K(18-c-6)]+[RH2P]- exists as a contact ion pair, [K(crypt-222)]+[RH2P]- exists as a solvent-separated ion pair in the solid state. Reaction of RH2P? with AgOTf afforded an unexpected product, a silver(I) phosphaalkene complex. (Chemical Equation Presented).