Categories: C-C Bond Formation > Oxygen-containing molecules > Carbonyl compounds >
Alkenylations
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Recent Literature
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 synergistic combination of copper and chiral amine catalysis enables an
enantioselective α-vinylation of aldehydes using vinyl iodonium triflate salts.
These mild catalysis provides enolizable α-formyl vinylic stereocenters without
racemization or olefin transposition. These high-value coupling adducts are
readily converted into various useful olefin synthons.
E. Skucas, D. W. C. MacMillan, J. Am. Chem. Soc., 2012,
134, 9090-9093.
A synergistic combination of copper and chiral amine catalysis enables an
enantioselective α-alkenylation of aldehydes using boronic acids. The merger of
two highly utilized and robust catalytic systems has allowed for the development
of a mild and operationally trivial protocol for the direct formation of
α-formyl olefins employing common building blocks for organic synthesis.
J. M Stevens. D. W. C. MacMillan, J. Am. Chem. Soc., 2013,
135, 11756-11757.
The use of gem-bis(boronates) as precursors enables a construction of
quaternary α-aryl aldehydes, in which both groups are installed simultaneously.
This methodology provides a general strategy to produce quaternary α-aryl
aldehydes with broad scopes and synthetic convenience. In addition, gem-bis(boronates)
are readily available from ketones.
P. Zheng, Y. Zhai, X. Zhao, T. Xu, Org. Lett.,
2019, 21, 393-396.
Intermolecular coupling of aromatic and aliphatic ketone lithium enolates with a
variety of alkenyl halides is achieved in good yields in the presence of Ni(cod)2
catalyst, an N-heterocyclic carbene (NHC) ligand, and LiI.
M. Grigalunas, T. Ankner, P.-O. Norrby, O. Wiest, P. Helquist, J. Am. Chem. Soc., 2015,
137, 7019-7022.
In a protocol for a mild, catalytic, intermolecular alkenylation of ketone
enolates, Pd/Q-Phos as catalyst enables an efficient intermolecular coupling of
various ketones with alkenyl bromides with a slight excess of LiHMDS at 0°C.
M. Grigalunas, T. Ankner, P.-O. Norrby, O. Wiest, P. Helquist, Org. Lett., 2014,
16, 3970-3973.
KOtBu/DMSO promoted α-vinylation of aliphatic, cycloaliphatic, and alkyl
aromatic (heteroaromatic) ketones with diverse arylacetylenes enables the
synthesis of various β,γ-unsaturated ketones of E configuration in very
good yields.
B. A. Trofimov, E. Y. Schmidt, N. V. Zorina, E. V. Ivanova, I. A. Ushakov, J. Org. Chem., 2012,
77, 6880-6886.
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 convenient and general atom transfer radical addition (ATRA) of simple
nitriles, ketones, and esters to alkynes provides a wide range of
β,γ-unsaturated nitriles, ketones, and esters.
Y. Xiao, Z.-Q. Liu,
Org. Lett., 2019, 21, 8810-8813.
An operationally simple and scalable Cu-catalyzed asymmetric conjugate
addition of trialkenylboroxines to enone diesters proceeded at
room temperature. Mechanistic studies revealed that two different catalytic
species work synergistically in the reaction.
K. Yasumoto, N. Kunitomo, T. Kano, Org. Lett., 2023, 25,
1497-1502.
Related
Multifunctional palladium catalysis allows a one-pot stereocontrolled synthesis
of tetrasubstituted methyl ketones and enynes. The homogeneous palladium
dihalide catalyst is used
for the bromo-/chloroallylation of alkynes and in situ for subsequent
Wacker-Tsuji oxidation or Sonogashira cross-coupling.
A. N. Thadani, V. H. Rawal, Org. Lett., 2002, 4,
4321-4323.