Categories: C-C Bond Formation > Oxygen-containing molecules > α,β-unsaturated compounds >
Synthesis of substituted α,β-unsaturated compounds
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Recent Literature
Iron-catalyzed cross-coupling of Grignard reagents with (E)- and (Z)-enol
tosylates proceeded smoothly to give a variety of the corresponding (E)-
and (Z)-trisubstituted α,β-unsaturated methyl esters in good yield. The
simple, mild, stereoretentive method utilized iron(III) chloride and other iron
salts as catalyst.
H. Nishikado, H. Nakatsuji, K. Ueno, R. Nagase, Y. Tanabe, Synlett, 2010,
2087-2092.
The reaction of alkynes with Ni(cod)2 and CO2 gave a nickelacycle, which was
reacted with various organozinc reagents under very mild conditions to provide
β,β‘-disubstituted, α,β-unsaturated carboxylic acids in a highly regio- and
stereoselective manner.
M. Takimoto, K. Shimizu, M. Mori, Org. Lett., 2001,
3, 3345-3347.
A Pd-catalyzed oxidative cross-coupling reaction of arylboronic acids with
α-diazoesters using molecular oxygen as the reoxidant gives E-α,β-diarylacrylates
in good yields and very high E-to-Z selectivity.
Y.-T. Tsoi, Z. Zhou, A. S. C. Chan, W.-Y. Yu, Org. Lett., 2010,
12, 4506-4509.
The combination of [Ru(p-cymene)Cl2]2/triethylphosphine/lithium
carbonate catalyzes a coupling of aryl bromides with unprotected 2-arylacrylic
acids to form (Z)-diarylacrylic acids in high yields. The reaction
tolerates a wide range of functional groups. The vinylic C-H activation proceeds
via base-assisted cyclometalation rather than a Heck-type mechanism, which
explains its stereoselectivity.
F. Belitz, A.-K. Seitz, J. F. Goebel, Z. Hu, L. K. Goossen, Org. Lett.,
2022, 24, 3467-3470.
An sp3 C-H bond-transformation reaction of methylarenes provides the
corresponding allylbenzene derivatives in good yields in the presence of
tetrabutylammonium iodide and tert-butyl hydroperoxide at 80 °C.
F. Shahsavari, A. Abbasi, M. Ghaznafarpour-Darjjani, S. M. Ghafelebashi, M.
Daftari-Besheli,
Synlett, 2017, 28, 1646-1648.
A practical, highly enantioselective reaction of readily available 1,3-dienes
and alkyl acrylates provides valuable, enantio-pure skipped 1,4-diene esters in
the presence of commercially available cobalt salts and chiral ligands. This
hetero-dimerization reaction tolerates various organic functional groups (e.g.,
aromatic substituents, halides, isolated mono- and di-substituted double bonds,
esters, silyl ethers, and silyl enol ethers).
S. M. Jing, V. Balasanthiran, V. Pagar, J. C. Gallucci, T. V. Rajanbabu, J. Am. Chem. Soc., 2017,
139, 18034-18043.
A ruthenium-catalyzed chelation-assisted C-H bond activation of aromatic ketones
followed by reaction with olefins provides Heck-type products in good to
excellent yields with a high regio- and stereoselective manner.
K. Padala, M. Jeganmohan, Org. Lett., 2011,
13, 6144-6147.
A copper-catalzed functionalization of propiolate esters with various Grignard
reagents in presence of trimethylsilyl trifluoromethanesulfonate enables the
synthesis of substituted E-vinyl silanes in good yields and excellent
diastereoselectivities via a catalytic carbocupration-silicon group migration
sequence.
A. J. Mueller Hendrix, M. P. Jennings, Org. Lett., 2010,
12, 2750-2753.
A stereoselective approach towards ethyl-substituted conjugated dienoic esters
utilising a Suzuki cross-coupling reaction has been achieved. In addition, a
method for their conversion into the corresponding ethyl ketones is presented.
D. Keck, T. Muller, S. Bräse, Synlett, 2006,
3457-3460.
A radical carbozincation of diethyl acetylenedicarboxylate in the presence of
air leads to fumaric derivatives through a selective alkylzinc group radical
transfer controlled by coordination. The total trans stereocontrol is
unprecedented, carbocupration is well-known to give the reversal selectivity at
low temperature, while classical radical addition methodologies lead to mixtures
of isomers.
J. Maury, L. Feray, M. P. Bertrand, Org. Lett., 2011,
13, 1884-1887.
An intermolecular reductive coupling of ynoates and aldehydes in the presence of
a silane using catalytic amounts of Ni(COD)2, an N-heterocyclic
carbene ligand, and PPh3 delivers invaluable silyl-protected
γ-hydroxy-α,β-enoates. This methodology provides a quick entry to many other
1,4-difunctional compounds and oxygen-containing five-membered rings. The
intermediacy of metallacycles in the catalytic process has been established.
S. K. Rodrigo, H. Guan, J. Org. Chem., 2012,
77, 8303-8309.
N-heterocyclic carbenes catalyze intramolecular β-alkylations of
α,β-unsaturated esters, amides, and nitriles that bear pendant leaving
groups to form a variety of ring sizes. The mechanism is discussed.
C. Fischer, S. W. Smith, D. A. Powell, G. C. Fu, J. Am. Chem. Soc.,
2006,
128, 1472-1473.
Highly regioselective Heck couplings of α,β-unsaturated tosylate and mesylate
derivatives with N-acyl N-vinylamines and vinyl ethers were
achieved. This method provides a cheap alternative to similar couplings using a
triflate electrophile.
A. L. Hansen, T. Skrydstrup, Org. Lett.,
2005,
7, 5585-5587.
A. L. Hansen, T. Skrydstrup, Org. Lett.,
2005,
7, 5585-5587.
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Copper-Catalyzed Conjugate Addition to α,β-Unsaturated Carbonyl Compounds |