Methyl 2-fluoroacrylate

• CAS: 2343-89-7
• Catalog Number: ACM2343897-1
• Category: Main Products
• Molecular Weight: 104.08g/mol
• Molecular Formula: C4H5FO2
• Synonyms: Methyl fluoroacrylate
• IUPAC Name: methyl 2-fluoroprop-2-enoate
• SMILES: COC(=O)C(=C)F
• InChI: InChI=1S/C4H5FO2/c1-3(5)4(6)7-2/h1H2,2H3
• InChI Key: ZTZJVAOTIOAZGZ-UHFFFAOYSA-N
• Melting Point: -42 I209°C
• Flash Point: 11°C
• Density: 1.114 g/mL
• Appearance: Colorless liquid
• Complexity: 97.9
• Covalently-Bonded Unit Count: 1
• EC Number: 607-233-2
• Exact Mass: 104.027358g/mol
• Formal Charge: 0
• H-Bond Acceptor: 3
• H-Bond Donor: 0
• Heavy Atom Count: 7
• Monoisotopic Mass: 104.027358g/mol
• Rotatable Bond Count: 2
• XLogP3: 1

Case Study

Methyl 2-Fluoroacrylate as a Fluoroalkene Source for the Stereoselective Synthesis of Trisubstituted Fluoroalkenes

Nouaille, Augustin, et al. Advanced Synthesis & Catalysis 363.8 (2021): 2140-2147.

Methyl 2-fluoroacrylate serves as an inexpensive liquid fluoroalkene source for ruthenium-catalyzed cross metathesis with terminal and internal alkenes, delivering trisubstituted fluoroalkenes that are valuable bioisosteres in medicinal and agrochemical research.
Experimental Protocol: The alkene partner at 0.25 mmol is combined with two equivalents of the fluoroacrylate and 1 mol% of a phosphine-containing ruthenium indenylidene precatalyst in dichloromethane, and the sealed mixture is stirred at 80 degrees Celsius for 15 h. Product yields and selectivities are determined by fluorine-19 nuclear magnetic resonance with an internal standard. The values are confirmed by isolation of the products.
Performance Evaluation: The model reaction achieves 94% nuclear magnetic resonance yield and 85% isolated yield with a 97:3 product to side-product ratio, exclusively furnishing the Z isomer. More than forty olefins are tolerated with yields from 36% to 98%, ring-opening metathesis of cyclooctene proceeds in 97% overall yield, and renewable fatty esters such as methyl oleate deliver the difunctionalized diester in 75% yield. No homodimer of the fluoroacrylate is observed, and side isomerization products remain below 11%. Turnover numbers up to 175 are unprecedented for fluoroalkene cross metathesis.

Methyl 2-Fluoroacrylate as a Fluorinated Michael Acceptor for the Domino Synthesis of Morita-Baylis-Hillman Analogues

Rasson, Corentin, et al. Chemistry-A European Journal 24.37 (2018): 9234-9237.

Methyl 2-fluoroacrylate functions as a fluorinated Michael acceptor in a copper-catalyzed one pot domino process combining borylation, aldolization and beta-fluoride elimination, enabling the formal addition of acrylates to carbonyl compounds to access Morita-Baylis-Hillman analogues, including substrates that are normally unreactive.
Experimental Protocol: Aldehydes at 1.5 equivalents react with the fluoroacrylate at 1 equivalent and bis(pinacolato)diboron at 1.5 equivalents in toluene at room temperature for 18 h in the presence of 2 mol% copper catalyst and 2 mol% diphosphine ligand, followed by treatment with 3.5 equivalents of sodium methoxide in methanol for 24 h. Ketone substrates are processed with 7 mol% of an N-heterocyclic carbene copper complex and 1.2 equivalents of the fluoroacrylate under the same conditions.
Performance Evaluation: Aldehyde-derived adducts are isolated in 64% to 99% yield, including 94% for a biaryl substrate and 99% for a simple alkyl aldehyde. Ketone-derived adducts, unprecedented for the classical reaction, are obtained in 38% to 98% yield, with a brominated acetophenone reaching 98%. The one pot sequence operates at room temperature throughout, avoiding harsh conditions typical of classical Morita-Baylis-Hillman reactions. The broad functional group tolerance and high efficiency demonstrate the utility of the process.

Methyl 2-Fluoroacrylate as a Fluorinated Dipolarophile for the Synthesis of beta-Fluoro-beta-proline

Yarmolchuk, Vladimir S., et al. Tetrahedron letters 52.12 (2011): 1300-1302.

Methyl 2-fluoroacrylate serves as a commercially available fluorinated dipolarophile in a concise three-step synthesis of beta-fluoro-beta-proline, a novel fluorinated analogue of beta-proline intended as a building block for peptide mimics and drug discovery programmes.
Experimental Protocol: An azomethine ylide is generated in situ from N-methoxymethyl-N-(trimethylsilylmethyl)benzylamine by addition of trifluoroacetic acid, and reacted with the fluoroacrylate in dry dichloromethane at room temperature for 4 h. The resulting pyrrolidine ester is hydrolyzed with one equivalent of sodium hydroxide in a methanol water mixture for 7 h. The benzyl group is removed by hydrogenation with palladium on charcoal under 20 atm of hydrogen at room temperature for 10 h.
Performance Evaluation: The key 1,3-dipolar cycloaddition provides the fluoropyrrolidine in 95% yield, hydrolysis proceeds in 75% yield and the final hydrogenolysis delivers the amino acid in 80% yield, giving an overall yield of 57% over three steps. No hydrogen fluoride elimination is observed during the synthesis, as evidenced by carbon 13 nuclear magnetic resonance data, and all derivatives are fully stable. Fmoc and Boc protected derivatives are obtained in 90% and 71% yield respectively for peptide applications.

Custom Q&A

What is the molecular formula of methyl 2-fluoroacrylate?

The molecular formula of methyl 2-fluoroacrylate is C4H5FO2.

When was methyl 2-fluoroacrylate created?

Methyl 2-fluoroacrylate was created on July 19, 2005.

How is the IUPAC name of methyl 2-fluoroacrylate computed?

The IUPAC name of methyl 2-fluoroacrylate is computed by Lexichem TK 2.7.0.

What is the Canonical SMILES of methyl 2-fluoroacrylate?

The Canonical SMILES of methyl 2-fluoroacrylate is COC(=O)C(=C)F.

What is the InChIKey of methyl 2-fluoroacrylate?

The InChIKey of methyl 2-fluoroacrylate is ZTZJVAOTIOAZGZ-UHFFFAOYSA-N.

What is the CAS number of methyl 2-fluoroacrylate?

The CAS number of methyl 2-fluoroacrylate is 2343-89-7.

How many hydrogen bond acceptor counts does methyl 2-fluoroacrylate have?

Methyl 2-fluoroacrylate has 3 hydrogen bond acceptor counts.

What is the topological polar surface area of methyl 2-fluoroacrylate?

The topological polar surface area of methyl 2-fluoroacrylate is 26.3 Å^2.

How many heavy atoms are present in methyl 2-fluoroacrylate?

There are 7 heavy atoms present in methyl 2-fluoroacrylate.

What is the formal charge of methyl 2-fluoroacrylate?

The formal charge of methyl 2-fluoroacrylate is 0.