27607-77-8 Usage
Chemical Properties
clear colourless to light brown fuming liquid
Physical properties
bp 45–47 °C/17 mmHg, 39–40 °C/12 mmHg;
d 1.225 g cm?3.
Uses
Different sources of media describe the Uses of 27607-77-8 differently. You can refer to the following data:
1. Trimethylsilyl Trifluoromethane?sulfonate is generally used following reactions:1. Silylation. TMSOTf is widely used in the conversion of car?bonyl compounds to their enol ethers. The conversion is some 109 faster with TMSOTf/triethylamine than with chlorotrimethy?lsilane.Dicarbonyl compounds are converted to the corresponding bis?enol ethers; this method is an improvement over the previous two?step method.In general, TMSOTf has a tendency toC-silylation which is seen most clearly in the reaction of esters, whereC-silylation dominates over O-silylation.2.Carbonyl Activation. 1,3-Dioxolanation of conjugated enals is facilitated by TMSOTf in the presence of 1,2-bis(trimethylsilyl?oxy)ethane. In particular, highly selective protection of sterically differentiated ketones is possible (eq 10).TMSOTf mediates a stereoselective aldol-type condensation of silyl enol ethers and acetals (or orthoesters). The nonbasic reaction conditions are extremely mild. The use of TMSOTf in aldol reactions of silyl enol ethers and ketene acetals with aldehydes is ubiquitous. Stereoselective cyclization of α,β-unsaturated enamide esters is induced by TMSOTf and has been used as a route to quinolizidines and indolizidines.3.The often difficult conjugate addition of alkynyl organometallic reagents to enones is greatly facilitated by TMSOTf. In particular, alkynyl zinc reagents (normally unreactive with α,β-unsaturated carbonyl compounds) add in good yield.The formation of nitrones by reaction of aldehydes and ketones with N-methyl-N,O-bis(trimethylsilyl)hydroxylamine is accelerated when TMSOTf is used as a catalyst; the acceleration is particularly pronounced when the carbonyl group is under a strong electronic influence.5. Methyl glucopyranosides and glycopyranosyl chlorides undergo allylation with allylsilanes under TMSOTf catalysis to give predominantly α-allylated carbohydrate analogs.Glycosidation is a reaction of massive importance and wide?spread employment. TMSOTf activates many selective glycosidation reactions.4.O-Silylation. The formation of TMS ethers can be achieved by reacting the requisite alcohol with TMSOTf and an amine (triethy?lamine, pyridine, or 2,6-lutidine) in dichloromethane;C-Silylation. Depending on the reaction conditions, sec?ondary amides can be either C-silylated or N-silylated;N-Silylation. The N-bis-silylation of α-amino acids with TMSOTf is only effective for glycine; for other α-amino acids N-mono-silylation prevails because the larger size of the carbon chain at the α-position hinders bis-silylation;C,O-Bis-silylation. Bis-silylation ofα,β-unsaturated carbonyl compounds can be achieved by palladium-TMSOTf-catalyzed addition of disilanes to enones, enals, or aromatic aldehydes via an η3-silyloxyallylpalladium intermediate;Carbonyl Activation. TMSOTf frequently acts as a Lewis acid and it is able to activate several functional groups (the car?bonyl group, the acetal unit, the nitrone moiety,…) thus facilitating different kinds of reactions;Acetal Activation. TMSOTf acts as a catalyst for the addi?tion of several nucleophiles (allylsilanes, allylstannanes, silyl enol ethers, trimethylsilyl cyanide) towardN,O-acetals;Nitrone Activation. The nucleophilic addition to aldonitrones depends on the nature of the metal involved and the presence/absence of an activator;Epoxide Ring Opening. One-pot alkylation-O-silylation re?actions of epoxides take place in excellent yields;Cleavage of Protecting Groups. THP ethers of primary, sec?ondary, and phenolic alcohols can be conveniently deprotected at room temperature; Hypervalent Iodine Chemistry. The formation of hyperva?lent iodine complexes is often promoted by TMSOTf.
2. Trimethylsilyl Trifluoromethanesulfonate is a trialkylsilyl triflate used as a catalyst in organic synthesis. Trimethylsilyl Trifluoromethanesulfonate is used in combination with boron trifluoride eth
yl ether to prepare a Lewis acid that is more powerful than its components and especially effective in acetonitrile solvent. Trimethylsilyl is a common reagent used in a Dieckmann-like cyclization of
ester-imides and diesters.
3. Catalyst and silylating agent for organic syntheses.
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)
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A New, Simple in Situ Preparation of Trimethylsilyl Trifluoromethanesulfonate
Ballester, Montserrat,Palomo, Antonio Luis
, p. 571 - 572 (1983)
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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).
