61550-02-5

Basic information

• Product Name: 2-(TRIMETHYLSILYLOXY)FURAN
• Synonyms: TRIMETHYLSILYLOXYFURAN;2-(TRIMETHYLSILOXY)FURAN;2-(TRIMETHYLSILYLOXY)FURAN;(2-FURANYLOXY)TRIMETHYLSILANE;2-(TRIMETHYLSILOXY)FURAN, STAB.;2-(Trimethylsilyloxy)furane;(2-Furyloxy)trimethylsilane;[(2-Furyl)oxy]trimethylsilane
• CAS NO: 61550-02-5
• Molecular Formula: C₇H₁₂O₂Si
• Molecular Weight: 156.25
• Product Categories: Monoalkoxysilanes;Si (Classes of Silicon Compounds);Silicon Compounds (for Synthesis);Si-O Compounds;Synthetic Organic Chemistry;Building Blocks;Furans;Heterocyclic Building Blocks
• Mol File: 61550-02-5.mol

Chemical Properties

• Boiling Point: 34-35 °C9 mm Hg(lit.)
• Flash Point: 76 °F
• Appearance: /
• Density: 0.929 g/mL at 25 °C(lit.)
• Vapor Pressure: 5.32mmHg at 25°C
• Refractive Index: n20/D 1.436(lit.)
• Storage Temp.: −20°C
• Solubility: sol most organic solvents, e.g. CH2Cl2, Et2O, benzene, THF, MeCN.
• BRN: 1423066
• CAS DataBase Reference: 2-(TRIMETHYLSILYLOXY)FURAN(CAS DataBase Reference)
• NIST Chemistry Reference: 2-(TRIMETHYLSILYLOXY)FURAN(61550-02-5)
• EPA Substance Registry System: 2-(TRIMETHYLSILYLOXY)FURAN(61550-02-5)

Safety Data

• Hazard Codes: F,Xi
• Statements: 11-36/37/38
• Safety Statements: 26
• RIDADR: UN 1993 3/PG 2
• WGK Germany: 3
• F: 10-21
• TSCA: No
• HazardClass: 3.2
• PackingGroup: III
• Hazardous Substances Data: 61550-02-5(Hazardous Substances Data)

Usage

Uses

Used in Synthetic Applications:
2-(TRIMETHYLSILYLOXY)FURAN is used as a synthetic reagent for the preparation of natural and synthetic furanones with anticancer activity. It is particularly useful in the formation of carbon-heteroatom bonds, alkylation, aldol-type reactions, conjugate addition, and Diels-Alder reactions, which are essential for the synthesis of complex organic molecules.
Used in Pharmaceutical Industry:
In the pharmaceutical industry, 2-(TRIMETHYLSILYLOXY)FURAN is used as a key intermediate in the synthesis of various drugs and drug candidates. Its ability to undergo multiple chemical reactions allows for the creation of diverse molecular structures with potential therapeutic applications.
Used in Chemical Research:
2-(TRIMETHYLSILYLOXY)FURAN is also utilized in chemical research as a model compound for studying various reaction mechanisms and exploring new synthetic pathways. Its unique reactivity and versatility make it an attractive candidate for investigating novel chemical transformations and developing innovative synthetic strategies.
Physical Properties:
2-(TRIMETHYLSILYLOXY)FURAN has a boiling point of 44-46 °C at a pressure of 17 mmHg and a density of 0.93 g/mL. These properties make it suitable for various synthetic applications and facilitate its handling and purification in laboratory settings.

Preparation

Accessible by silylation of 2(5H)-furanone, which is obtained at very low cost by oxidation of furfural.

Purification Methods

Fractionally distil it using a short path column. 1H NMR in CCl4 has : 4.90 (dd, J 1.3Hz, 3H), 6.00 (t, J 3Hz, 4H) and 6.60 (m, 5H). [Yoshii et al. Heterocycles 4 1663 1976.] 4-Trimethylsilyloxy-3-penten-2-one (cis) (acetylacetone enol trimethylsilyl ether) [13257-81-3] M 172.3, b 66-68o/4mm, 61-63o/5mm, d 4 0.917, n D 1.452. Fractionally distil it and store it in glass ampoules which are sealed under N2. It hydrolyses readily in contact with moisture giving, as likely impurities, hexamethyldisiloxane and 2,4-pentanedione. [West J Am Chem Soc 80 3246 1958, Beilstein 4 IV 4003.]

InChI:InChI=1/C7H12O2Si/c1-10(2,3)9-7-5-4-6-8-7/h4-6H,1-3H3

Upstream product

• 2786-02-9 2-lithiofuran 
• 5796-98-5 bis-trimethylsilanyl peroxide 
• 75-77-4 chloro-trimethyl-silane 
• 497-23-4 2-buten-4-olide 
• 996-50-9 N,N-diethyl-1,1,1-trimethylsilanamine 
• 27607-77-8 trimethylsilyl trifluoromethanesulfonate 
• 98-00-0 (2-furyl)methyl alcohol 
• 999-97-3 1,1,1,3,3,3-hexamethyl-disilazane 

Downstream Products

• 81112-85-8 5-(hydroxy(thiophen-2-yl)methyl)furan-2(5H)-one 
• 81112-86-9 5-[Hydroxy-(5-methyl-thiophen-2-yl)-methyl]-5H-furan-2-one 
• 81112-84-7 5-(1-hydroxy-3-phenylpropyl)furan-2(5H)-one 
• 111649-60-6 5-((E)-3-Phenyl-allyl)-5H-furan-2-one 
• 132047-01-9 5-O-(Trimethylsilyl)-6,7:8,9:10,11-tri-O-isopropylidene-2,3-dideoxy-D-arabino-L-altro-undec-2-enono-1,4-lactone 
• 132047-07-5 5-O-(Trimethylsilyl)-6,7:8,9:10,11-tri-O-isopropylidene-2,3-dideoxy-D-arabino-L-allo-undec-2-enono-1,4-lactone 
• 116859-07-5 E-7-methoxy-6-p-tolylthiohepta-2,6-dien-4-olide 
• 116859-07-5 Z-7-methoxy-6-p-tolylthiohepta-2,6-dien-4-olide 
• 116859-07-5 5-((Z)-3-Methoxy-2-p-tolylsulfanyl-allyl)-5H-furan-2-one 
• 123291-63-4 10-Hydroxy-9a-(5-oxo-2,5-dihydro-furan-2-yl)-9aH-anthracene-1,4,9-trione 
• 30336-14-2 5-butylfuran-2(5H)-one 
• 367-64-6 n-butyl trifluoroacetate 
• 18688-70-5 4-oxo-octanoic acid butyl ester 
• 124083-30-3 3-butylfuran-2(3H)-one 

Relevant articles and documents

Re-visiting the diastereoselectivity of organocatalytic conjugate addition of 2-trimethylsiloxyfuran to trans-crotonaldehyde

We describe the re-assignment of configuration previously ascribed to product diastereomers resultant from imidazolidinone-catalyzed conjugate addition of 2-trimethylsiloxyfuran to trans-crotonaldehyde. A modified procedure that uses a diphenylprolinol catalyst was subsequently developed to selectively provide the ‘syn’ diastereomeric product in high enantiomeric excess on decagram scales.

Facile and highly diastereoselective synthesis of 3-aminooxindoles via AgOAc-catalyzed vinylogous Mannich reaction

A novel AgOAc-catalyzed vinylogous Mannich reaction between easily prepared imines 1 derived from isatins and trimethylsilyloxyfuran 2 (TMSOF) was developed. This method provided a facile synthetic route to get access to synthetically useful quaternary 3-aminooxindole in excellent yields (94-99%) and diastereoselectivities (>99:1).

Stereoselective triplet-sensitised radical reactions of furanone derivatives

The stereo- and regioselectivity of triplet-sensitised radical reactions of furanone derivatives have been investigated. Furanones 7a,b were excited to the 3ππ* state by triplet energy transfer from acetone. Intramolecular hydrogen abstraction then occurred such that hydrogen was transferred from the tetrahydropyran to the β position of the furanone moiety. Radical combination of the tetrahydropyranyl and the oxoallyl radicals led to the final products 8a,b. In the intramolecular reaction, overall, a pyranyl group adds to the a position of the furanone. The effect of conformation was first investigated with compounds 9a,b carrying an additional substituent on the tether between the furanone and pyranyl moiety. Further information on the effect of conformation and the relative configuration at the pyranyl anomeric centre and the furanone moiety was obtained from the transformations of the glucose derivatives 12, 14, 17 and 18. Radical abstraction occurred at the anomeric centre and at the S′-position of the glucosyl moiety. Computational studies of the hydrogen-abstraction step were carried out with model structures. The activation barriers of this step for different stereoisomers and the abstraction at the anomeric centre and at the 6' -position of the tetrahydropyranyl moiety were calculated. The results of this investigation are in accordance with experimental observations. Furthermore, they reveal that the reactivity and regioselectivity are mainly determined in the hydrogen-abstraction step. Intramolecular hydrogen abstraction (almost simultaneous electron and proton transfer) in 3ππ * excited furanones only takes place under restricted structural conditions in a limited number of conformations that are defined by the relative configuration of the substrates. It is observed that in the biradical intermediate, back-hydrogen transfer occurs leading to the starting compound. In the case of glucose derivatives, this reaction led to epimerisation at the anomeric centre.

Preparation of silica supported tin chloride: As a recyclable catalyst for the silylation of hydroxyl groups with HMDS

Silica-supported tin chloride [SiO2-Sn(Cl)4-n] has been prepared by mixing tin chloride with activated silica gel in toluene under refluxing conditions for one day. Arange of primary, secondary, and tertiary alcohols as well as phenolic hydroxyl groups were converted into their corresponding trimethylsilyl ethers with hexamethyldisilazane in the presence of catalytic amounts of silica-supported tin chloride at room temperature. An excellent chemoselective silylation of hydroxyl groups in the presence of other functional groups was also observed. This catalyst could be recycled and reused fifteen times without loss of efficiency.

Total synthesis of (+)-azaspiracid-1. An exhibition of the intricacies of complex molecule synthesis

The synthesis of the marine neurotoxin azaspiracid-1 has been accomplished. The individual fragments were synthesized by catalytic enantioselective processes: A hetero-Diels-Alder reaction to afford the E- and HI-ring fragments, a carbonyl-ene reaction to furnish the CD-ring fragment, and a Mukaiyama aldol reaction to deliver the FG-ring fragment. The subsequent fragment couplings were accomplished by aldol and sulfone anion methodologies. All ketalization events to form the nonacyclic target were accomplished under equilibrating conditions utilizing the imbedded configurations of the molecule to adopt one favored conformation. A final fragment coupling of the anomeric EFGHI-sulfone anion to the ABCD-aldehyde completed the convergent synthesis of (+)-azaspiracid-1.

2,5-Dimethoxy-2,5-dihydrofuran chemistry: a new approach to 2(5H)-furanone derivatives

2,5-Dimethoxy-2,5-dihydrofuran is a synthetic equivalent of 2(5H)-furanone or 2-trimethylsilyloxyfuran, useful C4 synthons in the preparation of 5-substituted-2(5H)-furanone derivatives. The reaction conditions adopted allow to obtain different classes of complex and biologically interesting compounds, in only one step, with high yields.

Toward the development of a general chiral auxiliary. Enantioselective alkylation and a new catalytic asymmetric addition of silyloxyfurans: Application to a total synthesis of (-)-rasfonin

An enantioselective total synthesis of the apoptosis-inducing natural product, (-)-rasfonin, is described. Camphor lactam-mediated asymmetric alkylation reactions enabled the installation of three stereogenic centers with >95:5 diastereoselectivity. A modified Corey-Peterson olefination was employed in the construction of the (E,E)-diene system. A highly diastereoselective, asymmetric vinylogous Mukaiyama aldol addition was conducted using a chiral cationic oxazaborolidine catalyst. The pyranone core of the natural product was prepared via a DBU-promoted rearrangement of a furanol to its corresponding pyranol with concomitant [1,4]-silyl transfer. Copyright

Synthesis of furanone-based natural product analogues with quorum sensing antagonist activity

The synthesis of 5- and 3-(1′-hydroxyalkyl)-substituted 5H-furan-2-ones 4a-d and 8a-d as well as 5-alkylidene-5H-furan-2-ones 5a-d is described. A study of the structure-activity relationship of these furanone-based natural product analogues towards two different quorum sensing systems is reported. Although the synthesized compounds are not as potent quorum sensing inhibitors as some natural counterparts and a synthetic analogue hereof, interesting structure-activity relationships are seen.

Stereoselective synthesis of freelingyne and related γ-alkylidenebutenolides via vinylogous Mukaiyama aldol additions

Following the strategy of Scheme 1, a Mukaiyama aldol addition/anti-elimination route to stereopure γ-alkylidenebutenolides 4 was established. The addition giving 27 was only moderately diastereoselective but the products lk- and ul-27 were chromatographically separable (Scheme 4). They underwent highly selective anti-eliminations in the presence of triflic anhydride-pyridine or Burgess' reagent, furnishing the thiophene-containing butenolides Z- and E-28, respectively (Scheme 5). The Mukaiyama aldol addition leading to compound 29 was 100% lk-selective when mediated by BF3 etherate and 87 : 13 ul-selective in the presence of ZnBr2 (Scheme 6). Stephens-Castro couplings of the resulting butenolides lk- and ul-29 with 3-ethynylfuran proceeded with complete conservation of the stereochemical integrity (Scheme 7). The subsequent anti-eliminations of water were best realized by treatment with DEAD-PPh3. They provided freelingyne (Z-9) with ds = 92 : 8 and its isomer E-9 with ds = 98 : 2 (Scheme 8). Analogously, the differently substituted (trimethylsiloxy)furans 15 or 16 provided the freelingyne analogs Z-10, E-10 and Z-11 (Schemes 6-8).

Asymmetric synthesis of butenolide and butyrolactone derivatives

2-Trimethylsiloxyfuran and 4-methoxy-2-trimethylsiloxyfuran, which are readily prepared from butenolide and methyl tetronate respectively, have been reacted with a series of homochiral ortho-esters and oxazolidine derivatives in the presence of Lewis acids to afford homochiral 2(5H)-furanone derivatives. The structures of three products have been determined using nmr spectroscopy and, where possible, by X-ray analysis. Preliminary experiments have been carried out involving conjugate addition to these unsaturated lactones, demonstrating their potential as substrates for natural product synthesis.