Categories: C-C Bond Formation > Arenes >
Alkylation, Arylation
Name Reactions
Friedel-Crafts Acylation followed by Deoxygenation
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Versatile Cross Coupling Methods: Hiyama Coupling (R-X + R'-SiR''3) Hiyama-Denmark Coupling (R-X + R-SiMe2OH) Kumada Coupling (R-X + R'-MgX) Negishi Coupling (R-X + R'-ZnX) Stille Coupling (R-X + R'-SnR''3) Suzuki Coupling (R-X + R'-BY3) |
Recent Literature
Simple, cheap, and toxicologically benign iron salts turned out to be highly
efficient precatalysts for cross-coupling reactions of alkyl or aryl
Grignard reagents, zincates, or organomanganese species with aryl and
heteroaryl chlorides, triflates, and even tosylates. Aryl bromides and
iodides are prone to a reduction of their C-X bonds in the presence of the
iron catalyst. The exceptionally mild reaction conditions tolerate a series
of functional groups such as esters, ethers, nitriles, sulfonates,
sulfonamides, thioethers, acetals, alkynes, and -CF3 groups.
A. Fuerstner, A. Leitner, M. Méndez, H. Krause, J. Am. Chem. Soc.,
2002,
124, 13856-13863.
An iron-catalyzed cross-coupling reaction of a primary or secondary alkyl
halide with an aryl Grignard reagent proceeds under mild conditions to give
the corresponding coupled product in excellent yield.
M. Nakamura, K. Matsuo, S. Ito, E. Nakamura, J. Am. Chem. Soc.,
2004,
126, 3686-3687.
Various types of substrates were found to undergo effective cross-coupling
with Grignard reagents in the presence of a low-valent iron complex within
minutes even at -20°C.
R. Martin, A. Fuerstner, Angew. Chem., 2004,
116, 4045-4047.
Butylmethylimidazolium tetrachloroferrate (bmim-FeCl4) was found
to be a very effective and completely air stable catalyst for the biphasic
Grignard cross-coupling with primary and secondary alkyl halides bearing
α-hydrogens. The product was simply isolated in the ethereal layer and the
ionic liquid catalyst was successfully recycled four times.
K. Bica, P. Gaertner, Org. Lett.,
2006,
8, 733-735.
Suzuki cross-coupling reactions of an unprecedented array of unactivated
primary and secondary alkyl halides with arylboronic acids can be
accomplished through the use of nickel/amino alcohol-based catalysts. Both
the nickel precatalysts and the amino alcohols are commcercially available
and air-stable.
F. González-Bobes, G. C. Fu, J. Am. Chem. Soc.,
2006,
128, 5360-5361.
The use of [PdCl(C3H5)]2/cis,cis,cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane
as a catalyst allows the Suzuki coupling of a range of aryl bromides and
chlorides with alkylboronic acids in good yields. The functional group
tolerance on the aryl halide is remarkable. Furthermore, this catalyst can
be used at low loading, even for reactions of sterically hindered aryl
bromides.
I. Kondolff, H. Doucet, M. Santelli, Tetrahedron,
2004, 60, 3813-3818.
A novel method for the palladium-catalyzed cross-coupling of alkyl chlorides
and Grignard reagents has been developed. Good to excellent yields of the
coupling products were obtained at room temperature, and functional groups such
as ethers, esters, acetals, fluorides, nitriles, aryl and benzyl were tolerated.
A. C. Frisch, N. Shaikh, A. Zapf, M. Beller, Angew. Chem., 2002,
114, 4218-4221.
Screening of a 15-member library of phosphaadamantane ligands has allowed
for the rapid determination of the most suitable ligand for facilitating
Suzuki-type couplings of alkyl halides or tosylates containing β-hydrogens
with either boronic acids or alkylboranes.
T. Brenstrum, D. A. Gerristma, G. M. Adjabeng, C. S. Frampton, J. Britten,
A. J. Robertson, J. McNulty, A. Capretta, J. Org. Chem., 2004,
69, 7635-7639.
A versatile method has been developed for the cross-coupling of boronic
acids with unactivated alkyl electrophiles at room temperature. It has been
demonstrated that Pd(P(t-Bu)2Me)2 undergoes
oxidative addition under surprisingly mild conditions and that the resulting
adduct is sufficiently stable toward β-hydride elimination.
J. H. Kirchhoff, M. R. Netherton, I. D. Hill, G. C. Fu, J. Am. Chem. Soc.,
2002,
124, 13662-13663.
The superacid-catalyzed reaction of various olefinic amines and
related compounds with benzene gives addition products in good yields. The
formation of reactive, dicationic electrophiles is proposed.
Y. Zhang, A. McElrea, G. V. Sanchez, Jr., D. Do, A. Gomez, S. L . Aguirre, R. Rendy, D. A. Klumpp, J. Org. Chem., 2003,
68, 5119-5122.
Palladium catalyzed Suzuki-Miyaura coupling with aryl chlorides using a
bulky phenanthryl N-heterocyclic carbene ligand
C. Song, Y. Ma, Q. Chai, C. Ma, W. Jiang, M. B. Andrus, Tetrahedron, 2005,
61, 7438-7446.
Kinetic vs thermodynamic deprotonation studies on secondary and tertiary
sulfonamides using n-BuLi have been carried out. Application of the
developed conditions allows the synthesis of diverse sulfonamide products
(E=Me).
S. L. MacNeil, O. B. Familoni, V. Snieckus, J. Org. Chem, 2001,
66, 3662-3670.
By treatment with s-BuLi/TMEDA at -78°C, unprotected 2-methoxybenzoic
acid is deprotonated exclusively in the position ortho to the
carboxylate. A reversal of regioselectivity is observed when the acid is
treated with n-BuLi/t-BuOK.
T.-H. Nguyen, A.-S. Castanet, J. Mortier, Org. Lett.,
2006,
8, 765-768.
The mild cross-coupling reaction of alkyl- and arylmanganese reagents with
o-chloro- or o-bromoaryl ketones gives substituted ketones in high
yields with excellent chemoselectivity.
G. Cahiez, D. Luart, F. Lecomte, Org. Lett.,
2004,
6, 4395-4398.
The Rh-catalyzed cross-coupling between ArZnI and TMSCH2I
gave various functionalized benzylsilanes in good yields. A mechanism is
proposed.
H. Takahashi, K. M. Hossain, Y. Nishihara, T. Shibata, K. Takagi,
J. Org. Chem.,
2006,
71, 671-675.
An efficient method of constructing 4-benzyl piperidines and related
substances is described. This protocol tolerates a wide variation in both
reaction partners. The concise formation of a variety of building blocks,
such as those described here, has found wide applicability in our drug
discovery programs.
S. Vice, T. Bara, A. Bauer, C. A. Evans, J. Fort, H. Josien, S. McCombie, M.
Miller, D. Nazzareno, A. Palani, J. Tagat, J. Org. Chem,
2001, 66, 2487-2492.
The catalytic iridium-catalyzed 1,6-addition of aryl boronic acids to
electron-deficient dienes gave high yields of the corresponding δ-arylated
carbonyl compounds with perfect 1,6-selectivity.
T. Nishimura, Y. Yasuhara, T. Hayashi, Angew. Chem. Int. Ed.,
2006,
45, 5164-5166.
The superacid-catalyzed (triflic acid) reaction of olefinic amines and
related compounds with benzene gives addition products in good yields. A
reactive, dicationic species is reported.
Y. Zhang, A. McElrea, G. V. Sanchez, D. Do, A. Gomez, S. L . Aguirre, R.
Rendy, D. A. Klumpp, J. Org. Chem., 2003,
68, 5119-5122.
Superelectrophilic reactivity of α,β-unsaturated amides
towards weak nucleophiles such as arenes and cyclohexane is initiated either
with triflic acid or with excess AlCl3.
Condensation with aromatics in the presence of AlCl3
gives 3-arylpropionamides in excellent yields, while a selective ionic hydrogenation
of
some amides with cyclohexane gives
saturated amides.
K. Y. Koltunov, S. Walspurger, J. Sommer, Eur. J. Org. Chem., 2004,
4039-4047.
Novel chiral phosphine-olefin ligands have been designed, which acts as
bidentate 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.,
2005,
117, 4687-4690.
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.
A new approach to 2-(arylmethyl)aldehydes begins
with a silylformylation reaction of terminal acetylenes with aryl- or
heteroarylsilanes, followed by treatment of the products with TBAF to induce a 1,2-anionotropic
rearrangement of the aryl group.
L. A. Aronica, P. Raffa, A. M. Caporusso, P. Salvadori, J. Org.
Chem., 2003, 5, 9292-9298.
A new, stereoselective, palladium-catalyzed method for the synthesis of
substituted tetrahydrofurans from γ-hydroxy alkenes and aryl bromides forms
both a C-C and a C-O bond with diastereoselectivities of up to >20:1. The
reactions probably proceed via the intramolecular insertion of an olefin
into a Pd(Ar)(OR) intermediate.
J. P. Wolfe, M. A. Rossi, J. Am. Chem. Soc.,
2004,
126, 1620-1621.
The Rh-catalyzed reaction of 9-aryl-9-borabicyclo[3.3.1]nonanes with
α,β-unsaturated ketones and aldehydes gave high yields of tandem
1,4-addition-aldol reaction products with high syn selectivity. The
mechanism is discussed.
K. Yoshida, M. Ogasawara, T. Hayashi, J. Am. Chem. Soc., 2002,
124, 10984-10985.
