94041-88-0Relevant academic research and scientific papers
Decarboxylative Alkylcarboxylation of α,β-Unsaturated Acids Enabled by Copper-Catalyzed Oxidative Coupling
Gao, Bao,Xie, Yinjun,Shen, Zhiqiang,Yang, Lei,Huang, Hanmin
, p. 4968 - 4971 (2015/11/03)
A facile and general method for copper-catalyzed decarboxylative alkylcarboxylation of cinnamic acids with dimethyl 2,2′-azobis(2-methylpropionate) has been developed. The scope and versatility of the reaction was demonstrated, and a broad range of substrates bearing electron-donating and -withdrawing groups on the aromatic rings were all compatible with this reaction to provide desired β,γ-unsaturated esters in moderate to good yields. Moreover, α,β-unsaturated acids with a carbonyl group on the γ-position of acrylic acids also smoothly proceeded to furnish the desired products in good yields.
Gallium tribromide catalyzed coupling reaction of alkenyl ethers with ketene silyl acetals
Nishimoto, Yoshihiro,Ueda, Hiroki,Yasuda, Makoto,Baba, Akio
, p. 8073 - 8076 (2012/08/29)
A 'Ga'llant couple: The α-alkenylation of esters was accomplished by GaBr3-catalyzed coupling between alkenyl ethers and ketene silyl acetals. In this reaction system, various alkenyl ethers, including those with vinyl and substituted alkenyl groups, were applicable, and the scope of applicable ketene silyl acetals was sufficiently broad. The mechanism is also discussed. Copyright
Temperature-Dependent Alkylation of γ-Phenyl β,γ-Unsaturated Acid and Ester Systems in Hexamethylphosphortriamide-Tetrahydrofuran Solutions Using Lithium Diisopropylamide
Veen, Reinout H. van der,Cerfontain, Hans
, p. 342 - 346 (2007/10/02)
The reactivities of some β,γ-unsaturated carboxylic acids and their methyl esters toward alkylation with methyl iodide using the lithium diisopropylamide-hexamethylphosphortriamide (LDA-HMPT) systems in THF have been investigated.The methylation selectivity of pent-3-enoic acid (2) and (1,2-dihydro-3-naphtyl)acetic acid (6) on using 1.0 equiv. of methyl iodide is high, the α-mono- to α,α-dimethylation ratios at -78 deg C being >20.The selectivity is substantially lower for styrylacetic acid (4) and increases with increasing temperature from 2.3 at -78 deg C to 8.5 at -10 deg C.The occurrence of dimethylation is ascribed to intermolecular proton exchange between the monomethylated species IIa and the nonmethylated species Ia.For the β,γ-unsaturated esters the methylation selectivity is somewhat higher than that for the corresponding carboxylic acids.
PHOTOCHEMISTRY OF β,γ-UNSATURATED KETONES - V ; THE DIRECT IRRADIATION OF SOME γ-PHENYL β;γ-ENONES
Weerdt, Anton J. A. Van Der,Cerfontain, Hans
, p. 2121 - 2130 (2007/10/02)
The photochemistry of some members of the two series of γ-phenyl substituted acyclic β,γ-unsaturated ketones 1 and 2 upon direct irradiation with λ 310 nm has been investigated, viz 1c-1h and 2b+2c.The alkyl substituted (E)-5-phenyl-4-penten-2-ones 1c-1h yield the corresponding 1,3-acyl shift products and (Z)-isomers, and 1g and 1h in addition two decarbonylated products. 2b only yields the (Z)-isomer and some benzaldehyde, but 2c yields the 1,3-acyl shift product, the ODPM product, three hydrocarbons formed by disproportionation of the allyl radical, and some benzaldehyde.The β-phenyl β,γ-UK 3a proved to be photostable.The 1,3-acyl shift products of 1c-1h result mainly from the singlet excited state in a cage radical process.The exclusive formation of the (E)-configuration of the 1,3-acyl shift product is explained in terms of conformational preference of the intermediate allyl radical.It is proposed that the formation of the (Z)-isomer proceeds from 1T(?-?*) which is populated according to .Evidence is presented which supports the proposed mechanism.The β,γ-UK 2b containing a benzoyl moiety leads to a higher degree of (E)-(Z) isomerization than the corresponding 1d which has an acetyl moiety.The triplet energies of (E)- and (Z)-1h are 56 and ca 70 kcal/mol respectively.
