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1,4-Addition

Recent Literature

A mild and efficient Pd(II)-catalyzed conjugate addition of arylboronic acids to α,β-unsaturated carbonyl compounds, aldehydes, esters, and amides in the presence of 2,2'-bipyridine was developed. The mechanism and the role of the bipyridine are discussed.
X. Lu, S. Lin, J. Org. Chem., 2005, 70, 9651-9653.

Anionic four-electron donor-based palladacycles were highly efficient, practical catalysts for 1,4-additions of arylboronic acids with α,β-unsaturated ketones and 1,2-additions of arylboronic acids with aldehydes and α-ketoesters.
P. He, Y. Lu, C.-G. Dong, Q.-S. Hu, Org. Lett., 2007, 9, 343-346.

Palladium-phosphinous acids catalyze the microwave-assisted conjugate addition of arylsiloxanes to a wide range of α,β-unsaturated substrates in water. The described procedure eliminates the need for stoichiometric additives and an excess of arylsiloxane, and does not require an inert atmosphere.
R. Lerebours, C. Wolf, Org. Lett., 2007, 9, 2737-2740.

Ketone-, ester-, and amide-containing potassium trifluoroboratohomoenolates were prepared in good yields from the corresponding unsaturated carbonyl compounds. They are effective coupling partners in the Suzuki-Miyaura reaction with various electrophiles including electron-rich and electron-poor aryl bromides and -chlorides.
G. A. Molander, D. E. Petrillo, Org. Lett., 2008, 10, 1795-1798.

Conjugate addition of α,β-unsaturated ketones with arylzinc species, that were formed in situ from diethylzinc and a series of arylboronic acids by boron-zinc exchange reactions, gave 1,4-addition products in good yields.
L. Dong, Y.-J. Xu, L.-Z. Gong, A.-Q. Mi, Y.-Z. Jiang, Synthesis, 2004, 1015-1020.

A conjugate addition of various aryl halides and triflates to Michael acceptors is efficiently catalyzed by CoBr₂(2,2'-bipyridine). The described procedure allows for the synthesis of 1,4-addition products in good yields.
M. Amatore, C. Gosmini, J. Périchon, J. Org. Chem., 2006, 71, 6130-6134.

M. Amatore, C. Gosmini, J. Périchon, J. Org. Chem., 2006, 71, 6130-6134.

Various enantioenriched tert-butyl 3,3-diarylpropanoates are prepared via an asymmetric rhodium-catalyzed conjugate addition of arylboronic acids to unsaturated tert-butyl esters in the presence of chiral dienes as ligands.
J.-F. Paquin, C. R. J. Stephenson, C. Defieber, E. M. Carreira, Org. Lett., 2005, 7, 3821-3824.

The C₂-symmetric norbornadiene derivative (1R,4R)-2,5-dibenzylbicyclo[2.2.1]hepta-2,5-diene was used as ligand for the rhodium-catalyzed asymmetric 1,4-addition of organoboron and -tin reagents to α,β-unsaturated ketones, which gave high yields of the addition products with up to 99% enantioselectivity.
T. Hayashi, K. Ueyama, N. Tokunaga, K. Yoshida, J. Am. Chem. Soc., 2003, 125, 11508-11509.

An additive-free, clean conjugate addition reaction of organosiloxanes to α,β-unsaturated compounds is catalyzed by a cationic rhodium complex in dioxane/water. The mechanism involves a transmetalation step between the rhodium complex and the silicon reagent.
S. Oi, Y. Honma, Y. Inoue, Org. Lett., 2002, 4, 667-669.

A conjugate addition of organosiloxanes to α,β-unsaturated carbonyl compounds catalyzed by a cationic rhodium complex generated from [Rh(cod)(MeCN)₂]BF₄ and (S)-BINAP in dioxane/water gave products in good yields and excellent enantioselectivities.
S. Oi, A. Taira, Y. Honma, Y. Inoue, Org. Lett., 2003, 5, 97-99.

Rhodium-catalyzed conjugate addition of arylboronic acids to various 4-oxobutenamides provides oxobutanamides with high regio- and enantioselectivity and good yields in the presence of sterically demanding P-chiral diphosphines, such as Tangphos or Duanphos.
J. L. Zigterman, J. C. S. Woo, S. D. Walker, J. S. Tedrow, C. J. Borths, E. E. Bunel, M. M. Faul, J. Org. Chem., 2007, 72, 8870-8876.

The first enantioselective organocatalytic alkylation of electron-rich benzene rings with α,β-unsaturated aldehydes using iminium catalysis has provided a new strategy for the enantioselective construction of benzylic stereogenicity. The (2S,5S)-5-benzyl-2-tert-butylimidazolidinone amine catalyst has been found to mediate the conjugate addition of a wide variety of substituted and unsubstituted anilines to a diverse spectrum of unsaturated aldehydes.
N. A. Paras, D. W. C. MacMillan, J. Am. Chem. Soc., 2002, 124, 7894-7895.

A rhodium complex coordinated with (S,S)-2,5-dibenzylbicyclo[2.2.2]octa-2,5-diene (Bn-bod*) showed high catalytic activity and high enantioselectivity in the asymmetric 1,4-addition of arylboroxines α,β-unsaturated ketones.
F.-X. Chen, A. Kina, T. Hayashi, Org. Lett., 2006, 8, 341-344.

An enantioselective, rhodium-catalyzed 1,4-addition of arylboronic acids to β-silyl α,β-unsaturated carbonyl compounds has been developed employing (R,R)-Bn-bod* as a ligand, which allows the synthesis of various β-silyl 1,4-adducts in very high enantiomeric excess.
R. Shintani, K. Okamoto, T. Hayashi, Org. Lett., 2005, 7, 4757-4759.

Cu-catalyzed enantioselective conjugate additions of alkyl- and arylzinc reagents to unactivated cyclic β-substituted enones are promoted in the presence of 2.5-15 mol% of a readily available chiral NHC-based Cu complex, affording the desired products bearing all-carbon quaternary stereogenic centers in good yield and enantioselectivity.
K.-S. Lee, M. K. Brown, A. W. Hird, A. H. Hoveyda, J. Am. Chem. Soc., 2006, 128, 7182-7184.

The reaction of different functionalised organolithium compounds prepared by DTBB-catalysed lithiation of isochromane, phthalane, 2,3-dihydrobenzofuran and 1-chloro-3,3-diethoxypropane with an equimolecular amount of zinc bromide, followed by reaction with an aryl or an alkenyl bromide in the presence of a palladium catalyst gives the expected cross-coupling products.
M. Yus, J. Gomis, Eur. J. Org. Chem., 2002, 1989-1995.

Potassium trifluoro(organo)borates, which are highly stable and easily prepared organoboron derivatives, were able to react with various dehydroamino esters to alanine derivatives in good to high yields. This reaction, catalyzed by rhodium complexes, tolerates a great variety of amino protecting groups.
L. Navarre, S. Darses, J.-P. Genet, Eur. J. Org. Chem., 2004, 69-73.

Rhodium-catalyzed conjugate addition of potassium trifluoro(organo)borates to dehydroalanine derivatives, using chiral ligands such as fluorophos and in situ enantioselective protonation with guaiacol (2-methoxyphenol), afforded a variety of protected α-amino esters with high yields and enantiomeric excesses up to 95%.
L. Navarre, R. Martinez, J.-P. Genet, S. Darses, J. Am. Chem. Soc., 2008, 130, 6159-6169.

The precatalyst [{(P,R_s,R_s)-p-tol-BINASO}RhCl]₂, which can be synthesized from relatively cheap, commercially available starting materials, shows both excellent reactivity and selectivity in the asymmetric 1,4-addition of arylboronic acids to cyclic α,β-unsaturated ketones and esters.
R. Mariz, X. Luan, M. Gatti, A. Linden, R. Dorta, J. Am. Chem. Soc., 2008, 130, 2172-2173.

Novel chiral phosphine-olefin ligands have been designed, which act as bidentates in an efficient rhodium-catalyzed asymmetric 1,4-addition of aryl boronic acids to maleimides.
R. Shintani, W.-L. Duan, T. Nagano, A. Okada, T. Hayashi, Angew. Chem. Int. Ed., 2005, 44, 4611-4614.

R. Shintani, W.-L. Duan, T. Nagano, A. Okada, T. Hayashi, Angew. Chem. Int. Ed., 2005, 44, 4611-4614.