1968-40-7

Usage

Uses

Used in Flavor and Fragrance Industry:
Ethyl 4-pentenoate is used as a flavoring agent for its green fruity aroma. It is also used in the preparation of 5-iodomethyl-dihydro-furan-2-one by reacting with iodine.

Synthesis Reference(s)

The Journal of Organic Chemistry, 40, p. 2556, 1975 DOI: 10.1021/jo00905a041Synthetic Communications, 16, p. 1529, 1986 DOI: 10.1080/00397918608056406

InChI:InChI=1/C7H12O2/c1-3-5-6-7(8)9-4-2/h3H,1,4-6H2,2H3

Upstream product

• 591-80-0 pent-4-enoic acid 
• 64-17-5 ethanol 
• 39149-86-5 2-bromopent-4-enoic acid ethyl ester 
• 42367-85-1 bis-(5-ethoxycarbonyl-valeryl)-peroxide 
• 27126-42-7 ethyl 4-bromopentanoate 
• 109-89-7 diethylamine 
• 141-52-6 sodium ethanolate 
• 610-89-9 2-acetyl-pent-4-enoic acid ethyl ester 
• 74-86-2 acetylene 
• 1772-43-6 2,4,4-trimethyl oxazoline 
• 107-05-1 3-chloroprop-1-ene 
• 65500-21-2 2-(4,5-dihydro-thiazol-2-ylsulfanyl)-pent-4-enoic acid ethyl ester 
• 125456-38-4 ethyl 2-(allylsulfonyl)acetate 
• 78-39-7 Triethyl orthoacetate 

Downstream Products

• 16744-89-1 2-methylhex-5-en-2-ol 
• 132106-12-8 4-(4-isopropyl-phenyl)-valeric acid ethyl ester 
• 58848-57-0 4-(2-methoxy-5-methyl-phenyl)-valeric acid ethyl ester 
• 108667-62-5 4-(4-methoxy-3-methyl-phenyl)-valeric acid ethyl ester 
• 101740-99-2 4-(5-isopropyl-2-methyl-phenyl)-valeric acid ethyl ester 
• 14660-52-7 ethyl 5-bromovalerate 
• 168016-80-6 4,5-diamino-valeric acid ethyl ester 
• 34399-53-6 4-(2-methoxy-phenyl)-valeric acid ethyl ester 
• 857482-81-6 4-m-tolyl-valeric acid ethyl ester 
• 591-80-0 pent-4-enoic acid 
• 14594-25-3 ethyl 5-bromo-4-oxopentanoate 
• 10138-10-0 ethyl 4-oxobutanoate 
• 29493-00-3 dodec-6-ene 
• 74-85-1 ethene 

Relevant academic research and scientific papers

PREPARATION D'ESTERS γ-ETHYLENIQUES PAR ALLYLATION DU REACTIF DE REFORMATSKY EN PRESENCE DE SELS DE CUIVRE

The Reformatsky organozinc compounds react easily with allylic halides in the presence of copper salts.The reaction is stereoselective and can be made regioselective with a proper choice of reaction conditions.

Allyltris(trimethylsilyl)silane as Radical Allylating Agent for Organic Halides

Reaction of allyltris(trimethylsilyl)silane with organic halides under the free radical conditions resulted in allylation of the halides in moderate to good yields.The presence of three trimethylsilyl groups on the silicon could enhance the homolytic dissociation of a Si-C bond in the β-silylalkyl radical.

Efficient one-pot ring-opening/aldol reactions using (cyclopropyl) methylstannanes

(Cyclopropyl)methylstannanes, substituted with an electron-withdrawing group, have been found to be effective homoallylating reagents of aldehydes and ketones. The reaction proceeds by Lewis-acid catalyzed ring opening, followed by an aldol condensation of the resulting enolate, providing homoallylation products in excellent yields. The diastereoselectivity of the process was found to be highly dependent upon the temperature and the solvent, the reaction giving mainly anti adducts at -78°C and syn compounds at 0°C.

A New Route to the Prostaglandin Skeleton via Radical Alkylation. Synthesis of 6-Oxoprostaglandin E1

A new, mild, and efficient method for the construction of the prostanoid skeleton involving cuprate addition to α-(phenylseleno)cyclopentenones followed by radical-based coupling to the resulting products with allylstannane derivatives is described.The method is applied to the synthesis of 6-oxoprostaglandin E1, a biologically active and naturally occurring compound.

Solvent- and structure-dependent regioselectivity in the boron-mediated aldol reaction of 2-(1,3-dioxolan-2-yl)ethyl ethyl ketones

The regioselectivity of the Chx2BCl/Et3N-mediated (Chx = cyclohexyl) aldol reactions of ketones of general structure 2 has been studied and was shown to depend on both ketone structure and solvent. Useful levels of regioselectivity in favour of any of the two possible regioisomers were obtained in either pentane or diethyl ether. The relative configuration of the aldol products was assigned by 1H NMR studies of six-membered-ring derivatives. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.

Diastereoselective and Stereodivergent Synthesis of 2-Cinnamylpyrrolines Enabled by Photoredox-Catalyzed Iminoalkenylation of Alkenes

A photoredox-catalyzed iminoalkenylation of γ-alkenyl O-acyl oximes has been developed. Readily available alkenylboronic acids serve as alkenylation reagents, leading to densely functionalized pyrrolines. Both (E)- and (Z)-cinnamylpyrrolines are accessible depending on the reaction solvent. In dichloromethane, (E)-cinnamylpyrrolines are produced through a photoredox-mediated single-electron-transfer process. In tetrahydrofuran, (Z)-cinnamylpyrrolines are generated by photocatalytic contra-thermodynamic E-to-Z isomerization of (E)-cinnamylpyrrolines though an energy-transfer pathway. Two stereocenters are established with complete diastereoselectivity and only one diastereomer is isolated.

Scalable Microwave-Assisted Johnson-Claisen Rearrangement with a Continuous Flow Microwave System

We demonstrated the rapid Johnson-Claisen rearrangement of allyl alcohol and triethyl orthoacetate with a continuous flow apparatus combined with a microwave reactor. The reaction could be carried out without solvent, and only a catalytic amount of acetic acid was sufficient to promote the reaction under microwave irradiation conditions. To confirm the optimal reaction conditions found experimentally, we performed Design of Experiments (DoE) by the Nelder-Mead method and a least-squares method regarding the amount of acetic acid and the flow rate. Consequently, the highest yield of the desired γ,δ-unsaturated ester was obtained, and the productivity at the reaction step of the continuous process was 89.5 g/h under the optimal conditions, suggesting that 2.1 kg of the product would be theoretically obtained in 1 day. We also investigated the Johnson-Claisen rearrangement using other allylic alcohols, and the corresponding products were obtained in good to high yields per unit of time.

Palladium-Catalyzed Electrochemical Allylic Alkylation between Alkyl and Allylic Halides in Aqueous Solution

A new route for the direct cross-coupling of alkyl and allylic halides using electrochemical technique has been developed in aqueous media under air. Catalyzed by Pd(OAc)2, the Zn-mediated allylic alkylations proceed smoothly between a full range of alkyl halides (primary, secondary, and tertiary) and substituted allylic halides. Protection-deprotection of acidic hydrogen in the substrates is avoided.

Merger of Johnson-Claisen rearrangement and alkoxycarbonylation for atom efficient diester synthesis

The orthoester Johnson-Claisen rearrangement of allyl alcohol with triethyl orthoacetate for the synthesis of ethyl 4-pentenoate has been optimized, in order to allow for a selective and efficient subsequent alkoxycarbonylation using formates in an atom efficient manner. Diethyl adipate was successfully yielded in up to 89% applying very low orthoester excess, formic acid and mild reaction conditions in an innovative, one-pot procedure.

An improved solvent-free system for the microwave-assisted decarboxylation of malonate derivatives based on the use of imidazole

A comparative study of the thermal and microwave-assisted decarboxylation of a series of mono- and disubstituted monohydrolyzed malonate derivatives has been carried out. It has been found out that in both circumstances the use of imidazole has a profound effect on the success of the reaction. In general terms the assistance of microwave irradiation accelerates the decarboxylation process significantly and, at the same time, permits the use of minored temperatures with respect to the thermal via. It has been also found that both the thermal and the microwave-assisted transformation can be developed under solvent-free conditions.