Categories: C-C Bond Formation > Oxygen-containing molecules > Carboxylic Acids and Derivatives

Alkenylations

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Recent Literature

2-Chloroacetates as well as secondary and tertiary 2-chloroacetamides were successfully employed as electrophiles in the Suzuki-Miyaura cross-coupling reaction with potassium (E)- and (Z)-alkenyltrifluoroborates, affording the corresponding (E)- and (Z)-β,γ-unsaturated esters and amides in high yield.
G. A. Molander, T. Barcellos, K. M. Traister, Org. Lett., 2013, 15, 3342-3345.

A zinc- and photocatalyzed cross-coupling reaction of tetrafluoropyridine sulfides with vinyl halides provides β,γ-unsaturated esters. This reaction features a less-toxic and cost-effective nature.
M. K. Zaman, R. Li, W. Deng, J. Org. Chem., 2023, 88, 15761-15766.

A catalytic asymmetric cross-coupling of α-halo carbonyl compounds with aryl metal reagents generates synthetically useful α-aryl carboxylic acid derivatives in good enantiomeric excess. The method can also be applied to enantioselective alkenylation reactions.
X. Dai, N. A. Strotman, G. C. Fu, J. Am. Chem. Soc., 2008, 130, 3302-3303.

The reaction between aryl- or vinylboroxines with α-diazocarbonyl compounds offers an alternative approach for α-arylation and α-vinylation of carbonyl compounds. α-Arylated or α-vinylated carbonyl compounds are formed under mild conditions.
C. Peng, W. Zhang, G. Yan, J. Wang, Org. Lett., 2009, 11, 1667-1670.

A radical alkenylation reaction of α-halo carbonyl compounds with styrylindium dichloride as well as unactivated alkenylindiums proceeded in the presence of triethylborane. The geometry of the carbon-carbon double bonds was retained. Efficient one-pot strategies were developed.
K. Takami, H. Yorimitsu, K. Oshima, Org. Lett., 2004, 6, 4555-4558.

A kinetic-controlled photocatalyst-free visible-light-induced stereoselective synthesis of synthetically important α,α-gem-difluoro-Z-allyl esters was succeeded at room temperature in good yields and excellent Z-selectivity through a reductive radical ethoxycarbonyldifluoromethylation of terminal aryl alkynes with blue LED (465 nm)-excited Hantzsch ester.
J. Hao, W. Ding, Z. Zheng, L. Sun, J. Dong, M. Li, W. Wan, J. Org. Chem., 2022, 87, 13750-13756.

Phosphazene P4-tBu effectively catalyzes a nucleophilic substitution reaction of gem-difluoroalkenes with ketene silyl acetals under mild conditions to provide monofluoroalkenes possessing an alkoxycarbonylmethyl group in high yields with high Z selectivities.
A. Kondoh, K. Koda, M. Terada, Org. Lett., 2019, 21, 2277-2280.

An effient cobalt-catalyzed enantioselective vinylation of α-ketoesters, isatins, and imines delivers a range of synthetically useful allylic alcohols and amines in high enantiopurity. This convenient method employs commercially available and easy to handle catalysts and reagents.
Y. Huang, R.-Z. Huang, Y. Zhao, J. Am. Chem. Soc., 2016, 138, 6571-6576.

In a ligand-controlled cobalt-catalyzed regiodivergent alkyne hydroalkylation of terminal alkynes with alkyl halides, use of bisoxazoline and pyridine-oxazoline ligands provided (E)-1,2-disubstituted and 1,1-disubstituted alkenes with high E/Z stereoselectivity and regioisomeric ratio. Internal alkynes provide trisubstituted alkenes. The methods show excellent functional group compatibility.
Y. Li, D. Liu, L. Wan, J.-Y. Zhang, X. Lu, Y. Fu, J. Am. Chem. Soc., 2022, 144, 13961-13972.

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Substituted allylic zinc reagents, prepared via direct metal insertion in substituted allylic halides, react readily with a broad range of acid chlorides and chloroformates to yield the corresponding α-substituted β,γ-unsaturated ketones and esters in high yield and perfect regioselectivity.
C. Sämann, P. Knochel, Synthesis, 2013, 45, 1870-1876.