69739-34-0

Basic information

• Product Name: Trifluoromethanesulfonic acid tert-butyldimethylsilyl ester
• Synonyms: Methanesulfonic acid, trifluoro-, (1,1-dimethylethyl)dimethylsilyl ester;t-Butyldimethylsilyl triflate;t-butyldimethylsilyltrifluormethansulfonate;t-Butylmethylsilyl triflate;SILANE TBM2 TRIFLATE;T-BUTYLDIMETHYLSILYL TRIFLUOROMETHANESULFONATE;T-BUTYLDIMETHYLSILYLTRIFLUOROMETHANE-SULPHONATE;TBDMS TRIFLATE
• CAS NO: 69739-34-0
• Molecular Formula: C₇H₁₅F₃O₃SSi
• Molecular Weight: 264.34
• EINECS: 274-102-0
• Product Categories: Biochemistry;Protection & Derivatization Reagents (for Synthesis);Reagents for Oligosaccharide Synthesis;Si (Classes of Silicon Compounds);Silicon Compounds (for Synthesis);Silyl Esters;Si-O Compounds;Synthetic Organic Chemistry;metal triflate compounds
• Mol File: 69739-34-0.mol

Chemical Properties

• Melting Point: <0°C
• Boiling Point: 65-67 °C12 mm Hg(lit.)
• Flash Point: 98 °F
• Appearance: Clear colorless to yellow/Fuming Liquid
• Density: 1.151 g/mL at 25 °C(lit.)
• Vapor Pressure: 0.00137mmHg at 25°C
• Refractive Index: n20/D 1.385(lit.)
• Storage Temp.: 2-8°C
• Solubility: Slightly miscible with chloroform.
• Water Solubility: DECOMPOSES
• Sensitive: Moisture Sensitive
• BRN: 2370068
• CAS DataBase Reference: Trifluoromethanesulfonic acid tert-butyldimethylsilyl ester(CAS DataBase Reference)
• NIST Chemistry Reference: Trifluoromethanesulfonic acid tert-butyldimethylsilyl ester(69739-34-0)
• EPA Substance Registry System: Trifluoromethanesulfonic acid tert-butyldimethylsilyl ester(69739-34-0)

Safety Data

• Hazard Codes: C,F
• Statements: 10-34-37
• Safety Statements: 26-36/37/39-45-25-16
• RIDADR: UN 2920 8/PG 2
• WGK Germany: 3
• F: 10-21
• TSCA: No
• HazardClass: 3
• PackingGroup: III
• Hazardous Substances Data: 69739-34-0(Hazardous Substances Data)

Usage

Uses

Used in Organic Synthesis:
Trifluoromethanesulfonic acid tert-butyldimethylsilyl ester is used as a highly reactive silylating agent and Lewis acid for converting primary, secondary, and tertiary alcohols to their respective TBDMS ethers. It is also used to convert ketones and lactones into their enol silyl ethers, promoting conjugate addition of alkynylzinc compounds and triphenylphosphine to α,β-enones, activation of chromones in [4+2] cycloaddition reactions, rearrangement of allylic tributylstannyl silyl ethers, activation of pyridine rings toward Grignard reagents, transalkylation of tertiary amine N-oxides, and transformation of N-t-butoxycarbonyl groups into N-alkoxycarbonyl groups.
Used in Cope Rearrangement:
In the field of organic chemistry, Trifluoromethanesulfonic acid tert-butyldimethylsilyl ester is involved in the introduction of a bulky tert-butyl dimethylsilyl group onto a cis-bis(alkenyl)oxirane used in Cope rearrangement. It is associated with a thiolane and promotes the chalcogenide-Morita-Baylis-Hillman reaction.
Used in Enol Silyl Ether Preparation:
Trifluoromethanesulfonic acid tert-butyldimethylsilyl ester is used to prepare enol silyl ethers by reacting with ketones and lactones, which is an essential step in various organic synthesis processes.

Preparation

to 24 g (0.16 mol) of t-butyldimethylchlorosilane at 23°C under argon is added 14 mL (0.16 mol) of trifluoromethanesulfonic acid dropwise. The solution is heated at 60°C for 10 h, at which time no further hydrogen chloride evolves (removed through a bubbler). The resulting product is distilled under reduced pressure: 34 g (80% yield) of TBDMS triflate; bp 60°C/7 mmHg.

InChI:InChI=1/C17H22OSi/c1-17(2,3)19(18-4,15-11-7-5-8-12-15)16-13-9-6-10-14-16/h5-14H,1-4H3

Upstream product

• 18163-07-0 2-(trimethylsilyl)propene 
• 1493-13-6 trifluorormethanesulfonic acid 
• 29681-57-0 tert-butyldimethylsilane 
• 2923-28-6 silver trifluoromethanesulfonate 
• 18162-48-6 tert-butyldimethylsilyl chloride 
• 74472-22-3 allyl tert-butyldimethylsilane 
• 18173-64-3 tert-butyldimethylsilanol 
• 358-23-6 trifluoromethylsulfonic anhydride 

Downstream Products

• 72166-07-5 4'ξ-[(tert-butyl-dimethyl-silanyloxy)-methyl]-2'-cyclohexyl-3β-methoxy-(5α,16β,17β)-tetrahydro-androstano[17,16-e][1,2]oxazine-3'ξ-carbonitrile 
• 72166-06-4 4'ξ-[(tert-butyl-dimethyl-silanyloxy)-methyl]-2'-cyclohexyl-3β-methoxy-(5α,16β,17β)-tetrahydro-androstano[16,17-e][1,2]oxazine-3'ξ-carbonitrile 
• 72166-09-7 3β-acetoxy-4'ξ-[(tert-butyl-dimethyl-silanyloxy)-methyl]-2'-cyclohexyl-(5α,16β,17β)-tetrahydro-androstano[16,17-e][1,2]oxazine-3'ξ-carbonitrile 
• 124595-47-7 Acetic acid (2R,3S,4S,5R,6R)-3,5-diacetoxy-2-(tert-butyl-dimethyl-silanyloxymethyl)-6-phenylsulfanyl-tetrahydro-pyran-4-yl ester 
• 124595-41-1 Phenyl 2,3,4 tri-O-acetyl-6-O-TBDMS-1-thio-β-D-galactopyranoside 
• 124595-23-9 phenyl 2,3,4-tri-O-acetyl-6-O-tert-butyldimethylsilyl-1-thio-β-D-glucopyranoside 
• 137382-38-8 2-(tert-butyldimethylsilyl)-1,3-thiazole 
• 141510-40-9 3-(tert-butyldimethylsiloxy)-2-pyrone 
• 129192-24-1 3-Benzenesulfonyl-1-(tert-butyl-dimethyl-silanyloxy)-1-phenyl-decan-4-ol 
• 129192-23-0 2-Benzenesulfonyl-4-(tert-butyl-dimethyl-silanyloxy)-1,4-diphenyl-butan-1-ol 
• 129192-21-8 1-(tert-butyldimethylsilyloxy)-1-phenyl-3-phenylsulfonyl-4-pentanol 
• 129192-25-2 1-(tert-butyldimethylsilyloxy)-1-phenyl-3-phenylsulfonyl-5-methyl-4-hexanol 
• 116776-76-2 (2S,3S,4S)-3-(tert-Butyl-dimethyl-silanyloxy)-2,4-dimethyl-5-phenylsulfanyl-pentanoic acid methyl ester 
• 116825-36-6 (2S,3S,4R)-3-(tert-Butyl-dimethyl-silanyloxy)-2,4-dimethyl-5-phenylsulfanyl-pentanoic acid methyl ester 

Relevant articles and documents

A method to derivatize surface silanol groups to Si-alkyl groups in carbon-doped silicon oxides

A carbon-doped silicon oxide (CDO) finds use as a material with a low dielectric constant (k) for copper interconnects in multilayered integrated circuits (ICs). Hydrophilic silanol groups (Si-OH) on its surface, however, can attract moisture, thereby causing an undesirable increase in the dielectric constant. Modification of the exposed hydrophilic surface to a hydrophobic functional group provides one solution to this problem. We report here a strategy for converting surface Si-OH to hydrophobic silicon hydride (Si-H) without affecting the internal oxide network in CDO. The approach involves esterification of the exposed silanol to its triflate (silyltrifluoromethanesulfonate, Si-O-Tf), followed by reduction to Si-H with diisobutylaluminum hydride. Si-H is further modified by a photochemical reaction with an alkene (1-octadecene) to yield Si-R (R = -C18H37) to provide a more moisture resistant, and less polar Si-C as opposed to the Si-O backbone. Fourier transform infrared (FT-IR) spectroscopy, X-ray photoelectron spectrometry (XPS), and measurements of the contact angle with water substantiated the successful conversion. The reaction scheme is versatile, transforming silanol groups to silicon hydride in widely varying chemical sites, from small molecules to the surfaces of silica gels, SiOx and CDO wafers. A comparison with the films (self-assembled monolayers) derivatized with the octadecyltrichlorosilane indicated that the new method leads to a thicker (≈5 nm) but more loosely packed hydrocarbon film with slightly lower contact angles.

Diastereoselectivity in the boron aldol reaction of α-alkoxy and α,β-bis-alkoxy methyl ketones

In this work, using DFT calculations, we investigated the 1,4 and 1,5 asymmetric induction in boron enolate aldol reactions of α-alkoxy and α,β-bisalkoxy methyl ketones. We evaluated the steric influence of alkyl substituents at the α position and the stereoelectronic influence of the oxygen protecting groups at the α and β positions. Theoretical calculations revealed the origins of the 1,4 asymmetric induction in terms of the nature of the β-substituent. The synergistic effect between the α,β-syn and α,β-anti-bisalkoxy stereocenters was elucidated. In the presence of the β-alkoxy center, the reaction proceeds through the Goodman-Paton 1,5-stereoinduction model, experiencing a minor influence of the α-alkoxy center.

Chemoselective silyl transfer in the Mukaiyama aldol reaction promoted by super silyl Lewis acid

In the silyl Lewis acid-promoted Mukaiyama aldol reaction, the steric and electronic properties of the silyl group on the silyl Lewis acid influence the reaction mechanism and product distribution. When super silyl triflates such as (TMS)3SiOTf and (TES)3SiOTf are used as Lewis acids, the silyl group of the silyl enol ether chemoselectively transfers to the product. The mechanistic details have been investigated using density functional theory (DFT) calculations.

Thermodynamic stability and reactivity of silylated bis(oxy)iminium ions

(Chemical Equation Presented) Silylation of various nitronates with trialkylsilyl triflates was investigated by applying NMR techniques. In several cases, a flexible nitronate-bis(oxy)iminium ion (as an ion pair with triflate as counterion) equlibrium was found, and its thermodynamic parameters were determined. Elevation of temperature or dilution shifts this equilibrium toward the reactants. Activation parameters for the C,C-coupling reaction of silylated bis(oxy)iminium ions with a series of reference nucleophiles were determined. Estimated electrophilicity of bis(oxy)iminium ions allows one to count on C,C-coupling when partner nucleophilicity is N > 4.

Process for producing novel naphthyridine derivatives

A novel naphthyridine derivative showing high activity as a tachykinin receptor antagonist can be produced at high efficiency by reacting an acylating agent such as a carboxylic acid derivative with a compound represented by the formula (1): wherein R1, R2 and R3 represent independently a hydrogen atom, a lower alkyl group, a lower alkoxyl group, an aryl group, a heteroaryl group, an amino group, etc., and X1 and X2 represent respectively a halogen atom.

A non-enzymatic synthesis of (S)-(-)-rosmarinic acid and a study of a biomimetic route to (+)-rabdosiin

The synthesis of (S)-(-)-rosmarinic acid (30) in 9% overall yield is described. The synthesis was achieved by a convergent route in which 3-(3′,4′-dihydroxyphenyl)-(S)-lactic acid (23) and caffeic acid (25), both appropriately protected, were coupled to produce a pentaallyl precursor 29, which was then deprotected to give (S)-(-)-rosmarinic acid (30). A triallyl derivative 35 was similarly prepared and converted to (+)-rabdosiin (41) and its (1R,2S) isomer (42) via a biomimetic oxidative free radical coupling-cyclization followed by deallylation. The coupling-cyclization gave a ratio of rabdosiin diastereomers unlike that found in nature. A preliminary study showed that methyl (R)-mandelyl sinapate (15) could be dimerized diastereoselectively to give a 1,2-trans thomasidioate diester (16). The synthesis of (S)-(-)-rosmarinic aid (30) in 9% overall yield is described. The synthesis was achieved by a convergent route in which 3- (3',4'-dihydroxyphenyl)-(S)-lactic acid (23) and caffeic acid (25), both appropriately protected, were coupled to produce a pentaallyl precursor 29, which was then deprotected to give (S)-(-)-rosmarinic acid (30). A triallyl derivative 35 was similarly prepared and converted to (+)-rabdosiin (41) and its (1R,2S) isomer (42) via a biomimetic oxidative free radical coupling- cyclization followed by deallylation. The coupling-cyclization gave a ratio of rabdosiin diastereomers unlike that found in nature. A preliminary study showed that methyl (R)-mandelyl sinapate (15) could be dimerized diastereoselectively to give a 1,2-trans thomasidioate diester (16).

1,2,4-trioxane compounds having antimalarial activity

Novel 1,2,4-trioxanes which possess anti-malarial activity.

Enanthiospecific synthesis of longiborneol and longifolene

A trimethylsilyl enol ether (34) derived from camphor (1) undergoes intramolecular Mukaiyama reaction to provide a tricyclic ketone (36) that can serve as a key intermediate in a new enantiospecific synthesis of longiborneol (11) and longifolene (12).

NEW METHOD FOR THE PREPARATION OF t-BUTYLDIMETHYLSILYL TRIFLATE

t-Butyldimethylsilyl triflate is easily prepared from the reaction of triflic acid with isopropenyltrimethylsilane.

REAGENTS AND SYNTHETIC METHODS 55. NEW METHODS FOR THE PREPARATION OF t-BUTYLDIMETHYLSILYL TRIFLATE AND TRIMETHYLSILYL TRIFLATE.

An expeditious synthesis of t-butyldimethylsilyl triflate is described from triflic acid and t-butyldimethylsilane.Reaction between trichloromethyltrimethylsilane and triflic acid is also reported.