Categories: C-C Bond Formation > Arenes >
Alkylation, Arylation
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Recent Literature
A Pd-catalyzed direct methylation of aryl, heteroaryl, and vinyl boronate esters
with iodomethane occurs with a remarkably broad scope and is suitable for
late-stage derivatization of biologically active compounds.
A. M. Haydl, J. F. Hartwig, Org. Lett., 2019, 21,
1337-1341.
Activation of photochemically inert alkyl boronic esters by radicals
generated from alkylamines enables their use as cross-coupling partners for aryl
halides in dual photoredox/nickel catalysis mediated by visible light. This
mild, fast, and air-stable reaction offers an outstanding functional group
tolerance and allows quick access to relevant scaffolds for organic synthesis
and medicinal chemistry.
E. Speckmeier, T. C. Maier, J. Am. Chem. Soc.,
2022, 144, 9997-10005.
An efficient cobalt-catalyzed alkylation of aromatic Grignard reagents is
performed in good yields in the presence of CoCl2/TMEDA (1:1) as
catalytic system. Primary and secondary cyclic or acyclic alkyl bromides were
used successfully. The reaction tolerates ester, amide, and keto groups, is
inexpensive and very easy to carry out on a larger scale.
G. Cahiez, C. Chaboche, C. Duplais, A. Moyeux, Org. Lett., 2009,
11, 277-280.
A slow and regular addition of primary alkyl and aryl Grignard reagent
enables a high-yielding copper-catalyzed alkylation with alkyl bromides in the
absence of ligands. With secondary and
tertiary alkyl Grignard reagents, the presence of benzonitrile as a very simple
ligand is sufficent. A copper-catalyzed alkylation of organolithium compounds
was also studied.
G. Cahiez, O. Gager, J. Buendia, Synlett, 2010,
299-303.
The use of catalytic amounts of iron(III) fluoride and
1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene (SIPr) enables high-yielding
cross-coupling reactions of various combinations of aryl chlorides and alkyl
Grignard reagents including methylmagnesium bromide.
R. Agata, T. Iwamoto, N. Nakagawa, K. Isozaki, T. Hatakeyama, H. Takaya, M.
Nakamura,
Synthesis, 2015, 47, 1733-1740.
A simple, efficient and high-yielding iron-catalyzed cross-coupling reaction of
various primary, secondary, and tertiary alkyl chlorides with aryl Grignard
reagents was achieved by using N-heterocyclic carbene ligands. A wide
range of industrially abundant chloroalkanes can be converted, including
polychloroalkanes, which are challenging substrates under conventional
cross-coupling conditions.
S. K. Ghorai, M. Jin, T. Hatakeyama, M. Nakamura, Org. Lett., 2012,
14, 1066-1069.
The Pd-catalyzed cross-coupling of aryl bromides or triflates with
cyclopropylmagnesium bromide in the presence of substoichiometric amounts of
zinc bromide produces cyclopropyl arenes in very good yields. The cross-coupling
of other alkyl, cycloalkyl, and aryl Grignard reagents with aryl bromides under
the same conditions gives the corresponding substituted arenes in good yields.
C. Shu, K. Sidhu, L. Zhang, X.-j. Wang, D. Krishnamurthy, C. H. Senanayake, J. Org. Chem., 2010,
75, 6677-6680.
Mild Negishi Cross-Coupling Reactions Catalyzed by Acenaphthoimidazolylidene
Palladium Complexes at Low Catalyst Loadings
Z. Liu, N. Dong, M. Xu, Z. Sun, T. Tu, J. Org. Chem., 2013,
78, 7436-7444.
The combination of anodic preparation of alkoxy triphenylphosphonium ion and
nickel-catalyzed cathodic reductive cross-coupling enables an efficient method
to construct C(sp2)-C(sp3) bonds, in which free alcohols
and aryl bromides can be directly used as coupling partners.
Z. Li, W. Sun, X. Wang, L. Li, Y. Zhang, C. Li, J. Am. Chem. Soc.,
2021, 143, 3586-3543.
Bu4NI as additive accelerates the palladium(0)-catalyzed
cross-coupling between benzylic zinc bromides and aryl or alkenyl triflates.
Remarkably, it further enables a new nickel(0)-catalyzed cross-coupling between
functionalized benzylic zinc reagents and primary alkyl iodides under mild reaction conditions.
M. Piber, A. E. Jensen, M. Rottländer, P. Knochel,
Org. Lett., 1999, 1, 1323-1326.
Ball-milling enables a nickel-catalyzed cross-electrophile coupling of aryl
halides and alkyl halides. Under a mechanochemical manifold, the reductive C-C
bond formation was achieved in the absence of bulk solvent and air/moisture
sensitive setups, in reaction times of 2 h. The mechanical action provided by
ball milling permits the use of a range of zinc sources to turnover the nickel
catalytic cycle.
A. C. Jones, W. I. Nicholson, J. A. Leitch, D. L. Browne, Org. Lett., 2021, 23, 6337-6341.
5-Cyanoimidazole was identified as an inexpensive ligand for nickel-catalyzed
cross-electrophile couplings for the preparation of various alkylated arene
products with good yields. Furthermore, the scope of reductive couplings could
be expanded to challenging substrates, such as sterically hindered neopentyl
halides.
S. Biswas, B. Qu, J.-N. Desrosiers, Y. Choi, N. Haddad, N. K. Yee, J. J.
Song, C. H. Senanayake, J. Org. Chem., 2020, 85,
8214-8220.
Alkyl bromides can be coupled with aryl or heteroaryl bromides in excellent
yields in the presence of commercially available tris(trimethylsilyl)silane and
a metallaphotoredox catalyst. It is hypothesized that a photocatalytically
generated silyl radical species can perform halogen-atom abstraction to activate
alkyl halides as nucleophilic cross-coupling partners.
P. Zhang, C. Le, D. W. C. MacMillan, J. Am. Chem. Soc., 2016,
138, 8084-8087.
A cross-coupling reaction of functionalized arylmagnesium halides with
functionalized primary alkyl iodides and benzylic bromides in the presence of
catalytic CuCN·2LiCl provides coupled products in good yields at low
temperatures. In a transmetalation with stoichiometric CuCN·2LiCl and P(OMe)3
as additive, the resulting arylcopper species are stable at 20°C.
W. Dohle, D. M. Lindsay, P. Knochel,
Org. Lett., 2001, 3, 2871-2873.
An efficient reaction of unactivated and cheap alkyl chlorides in the presence
of indium and LiI provides alkyl indium species, that effectively underwent
palladium-catalyzed cross-coupling reactions with aryl halides with wide
functional group tolerance.
B.-Z. Chen, M.-L. Zhi, C.-X. Wang, X.-Q. Chu, Z.-L. Shen, T.-P. Loh, Org. Lett.,
2018, 20, 1902-1905.
A palladium-catalyzed cross-coupling reaction of alkyl-, vinyl-, alkynyl-,
and arylindium compounds with vinyl and aryl triflates or iodides proceeds in
excellent yields and high chemoselectivity without any excess of the
organometallic. Remarkably, indium organometallics transfer efficiently all organic groups attached to the metal.
I. Pérez, J. P. Sestelo, L. A. Sarandeses,
Org. Lett., 1999, 1, 1267-1269.
Hypercoordinate silicates represent an improved class of radical precursors for
single-electron transmetalation because of their low oxidation potentials and
the innocuous byproducts generated upon oxidation. The cross-coupling of
secondary and primary ammonium alkylsilicates with (hetero)aryl bromides works
in good to excellent yields.
M. Jouffroy, D. N. Primer, G. A. Molander, J. Am. Chem. Soc., 2016,
138, 475-478.
Stereospecific Pd-Catalyzed Cross-Coupling Reactions of Secondary Alkylboron
Nucleophiles and Aryl Chlorides
L. Li, S. Zhao, A. Joshi-Pangu, M. Diane, M. R. Biscoe,
J. Am. Chem. Soc., 2014,
136, 14027-14030.
Single-electron-mediated alkyl transfer enables a cross-coupling of secondary
alkyltrifluoroborates with an array of aryl bromides under mild conditions. The
reaction is mediated by an Ir photoredox catalyst and a Ni cross-coupling
catalyst.
D. N. Primer, I. Karakaya, J. C. Tellis, G. A. Molander, J. Am. Chem. Soc., 2015,
137, 2195-2198.
OBBD (B-alkyl-9-oxa-10-borabicyclo[3.3.2]decane) derivatives are easily made and
can be used for Suzuki-Miyaura couplings under mild aqueous micellar catalysis
conditions. Reaction medium recycling exemplifies the synthetic utility of this
technology.
N. R. Lee, R. T. H. Linstadt, D. J. Gloisten, F. Gallou, B. H. Lipshutz, Org. Lett.,
2018, 20, 2902-2905.
Chiral secondary organoboronic esters, when activated with t-butyllithium,
undergo efficient stereoretentive transmetalation with either zinc acetate or
zinc chloride. The organozinc compounds were found to engage in stereospecific
reactions with difluorocarbene, catalytic cross-couplings with palladium-based
catalysts, and trifluoromethylation with a copper(III) complex.
H. Liang, J. P. Morken, J. Am. Chem. Soc.,
2023, 145, 9976-9981.
A dimeric Ni(I) catalyst and an exogenous alkoxide base promote
Markovnikov-selective hydroarylation (alkenylation) of unactivated and activated
olefins using organo bromides or triflates derived from widely available phenols
and ketones. Products bearing aryl- and alkenyl-substituted tertiary and
quaternary centers could be isolated in very good yield and excellent
regioisomeric ratios.
C.-F. Liu, X. Luo, H. Wang, M. J. Koh, J. Am. Chem. Soc.,
2021, 143, 9498-9506.
Palladium-catalyzed decarbonylative alkylation reactions of acyl fluorides with alkylboranes having β-hydrogens
enable (sp2)-C(sp3) bond formation
via a highly efficient decarbonylative process. A wide range of
functional groups were well tolerated, even at the high temperature required for
decarbonylation.
L. Fu, Q. Chen, Z. Wang, Y. Nishihara,
Org. Lett., 2020, 22, 2350-2353.
Cross-coupling of redox-active esters (both isolated and derived in situ from
carboxylic acids) with organozinc and organomagnesium species using an Fe-based
catalyst system originally developed for alkyl halides is scalable and
sustainable.
F. Toriyama, J. Cornella, L. Wimmer, T.-G. Chen, D. D. Dixon, G. Creech, P. S.
Baran, J. Am. Chem. Soc., 2016,
138, 11132-11135.
In a decarboxylative coupling of alkyl N-hydroxyphthalimide esters with
aryl iodides in the presence of a nickel catalyst and Zn as reducing agent, no
photocatalyst, light, or arylmetal reagent is needed to form alkyl radicals from
the carboxylic acid derivative. Methyl, primary, and secondary alkyl groups can
all be coupled in good yield.
K. M. M. Huihui, J. A. Caputo, Z. Melchor, A. M. Olivares, A. M. Spiewak, K. A.
Johnson, T. A. DiBenedetto, S. Kim, L. K. G. Ackerman, D. J. Weix, J. Am. Chem. Soc., 2016,
138, 5016-5019.
Iodine-catalyzed direct indium insertions into alkyl iodide and bromides provide
alkyl indium reagents, that effectively underwent Pd-catalyzed cross-coupling
reactions with various aryl halides, exhibiting good compatibility to a variety
of sensitive functional groups.
M.-L. Zhi, B.-Z. Chen, W. Deng, X.-Q. Chu, T.-P. Loh, Z.-L. Shen, J. Org. Chem., 2019, 84,
3017-3023.
A Concise and Atom-Economical Suzuki-Miyaura Coupling Reaction Using
Unactivated Trialkyl- and Triarylboranes with Aryl Halides
H. Li, Y.-L. Zhong, C.-y. Chen, A. E. Ferraro, D. Wang, Org. Lett.,
2015,
17, 3616-3619.
Nickel-Catalyzed Negishi Cross-Coupling Reactions of Secondary Alkylzinc
Halides and Aryl Iodides
A. Joshi-Pangu, M. Ganesh, M. R. Biscoe, Org. Lett., 2011,
13, 1218-1221.
Zn-Mediated, Pd-Catalyzed Cross-Couplings in Water at Room Temperature
Without Prior Formation of Organozinc Reagents
A. Krasovskiy, C. Duplais, B. H. Lipshutz, J. Am. Chem. Soc., 2009,
131, 15592-15593.
Palladium complexes derived from air-stable secondary phosphine oxides or
chlorides enabled challenging Kumada-Corriu cross-couplings of unactivated alkyl
chlorides bearing β-hydrogens and proved applicable to transformations of
alkyl-substituted organometallics.
L. Ackermann, A. R. Kapdi, C. Schulzke, Org. Lett., 2010,
12, 2298-2301.
A room-temperature Ni-catalyzed reductive coupling of aryl bromides with
secondary alkyl bromides provides products in good to excellent yields. Slight
modification of this protocol allows efficient coupling of activated aryl
chlorides with cyclohexyl bromide and aryl bromides with allylic acetate.
S. Wang, Q. Qian, H. Gong, Org. Lett., 2012,
14, 3352-3355.
In the presence of a Ni catalyst and Zn, various aryl and vinyl bromides are
reductively coupled with alkyl bromides in high yields. Under similar conditions,
activated aryl chlorides can also be coupled with bromoalkanes. The protocols
are highly functional-group tolerant, and the reactions are assembled on the
benchtop with no special precautions to exclude air or moisture.
D. A. Everson, B. A. Jones, D. J. Weix, J. Am. Chem. Soc., 2012,
134, 6146-6159.
An efficient, nickel-catalyzed direct reductive cross-coupling of equimolar
amounts of alkyl halides with aryl halides in the presence of manganese is
generally high-yielding, highly functional-group-tolerant, and easy to perform.
The reaction appears to avoid the formation of intermediate organomanganese
species, and a synergistic effect was found when a mixture of two ligands was
employed.
D. A. Everson, R. Shrestha, D. J. Weix, J. Am. Chem. Soc., 2010,
132, 920-921.
An operationally simple cross-coupling reaction between aryl halides and alkyl
halides with high selectivity utilizes CoCl2/Me4-DACH as a
catalyst system. The underlying domino process exhibits high sustainability as
it obviates the need for the pre-formation and handling of stoichiometric
amounts of hazardous Grignard compounds.
W. M. Czaplik, M. Mayer, A. J. von Wangelin, Synlett, 2009,
2931-2934.
An operationally simple and user-friendly Ni-catalyzed reductive deaminative
arylation at unactivated sp3 carbon centers exhibits an excellent
chemoselectivity profile and broad substrate scope. The reaction has also been
used in the context of late-stage functionalization to reliably generate
structure diversity with amine-containing drugs.
R. Martin-Montero, Y. R. Yatham, H. Yin, J. Davies, R. Martin,
Org. Lett., 2019, 21, 2947-2951.
The alkylation of aryl sulfamates and carbamates using iron catalysis provides
synthetically useful yields across a range of substrates. The directing group
ability of sulfamates and carbamates, accompanied by their low reactivity toward
conventional cross-couplings, renders these substrates useful for the synthesis
of polyfunctionalized arenes.
A. L. Silberstein, S. D. Ramgren, N. K. Garg, Org. Lett., 2012,
14, 3796-3799.
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.
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. Int. Ed., 2004, 43,
3955-3957.
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.
The combination of a Ni catalyst with TDAE as sacrificial reductant enables a
dicarbofunctionalization of a broad range of olefins with two electrophilic carbon sources under reductive
conditions via simultaneous formation of one C(sp3)-C(sp3) and one C(sp3)-C(sp2) bond with exquisite selectivity.
W. Shu, A. García-Domínguez, M. T. Quirós, R. Mondal, D. J. Cárdenas, C.
Nevado, J. Am. Chem. Soc.,
2019, 141, 13812-13821.
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.
Iron-catalyzed cross-coupling of primary and secondary alkyl sulfonates with
arylzinc reagents, prepared from the corresponding aryllithium or magnesium
reagents with ZnI2, proceeds smoothly in the presence of excess TMEDA
and a concomitant magnesium salt.
S. Ito, Y.-i. Fujiwara, E. Nakamura, M. Nakamura, Org. Lett., 2009,
11, 4306-4309.
A Ni-catalyzed process for the cross-coupling of tertiary alkyl nucleophiles and
aryl bromides is extremely general for a wide range of electrophiles and
generally occurs with little isomerization. The same procedure also accommodates
the use of aryl triflates, vinyl chlorides, and vinyl bromides as the
electrophilic component.
A. Joshi-Pangu, C.-Y. Wang, M. R. Biscoe, J. Am. Chem. Soc., 2011,
133, 8478-8481.
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.
Palladium-catalyzed Negishi cross-coupling involving primary and secondary
alkyls, even in the presence of β-H, can be achieved using chelating phosphine
ligands containing an electron-deficient olefin. The superior effects of the
ligands were shown not only in the desired cross-coupling product yields but
also in the fast reaction at mild conditions.
X. Luo, H. Zhang, H. Duan, Q. Liu, L. Zhu, T. Zhang, A. Lei, Org. Lett., 2007,
9, 4571-4574.
Negishi Coupling of Secondary Alkylzinc Halides with Aryl Bromides and
Chlorides
C. Han, S. L. Buchwald, J. Am. Chem. Soc., 2009,
131, 7532-7533.
A CoCl2·2LiCl-catalyzed cross-coupling of diarylmanganese reagents
with secondary alkyl iodides provides the cross-coupling products in good yield
without rearrangements to unbranched products. High diastereoselectivities can
be reached.
M. S. Hofmayer, J. M. Hammann, D. Haas, P. Knochel, Org. Lett.,
2016, 18, 6456-6459.
"Bulky-Yet-Flexible" α-Diimine Palladium-Catalyzed Reductive Heck
Cross-Coupling: Highly Anti-Markovnikov-Selective Hydroarylation of Alkene in
Air
X.-W. Yang, D.-H. Li, A.-X. Song, F.-S. Liu, J. Org. Chem., 2020, 85,
11750-11765.
In the presence of a chiral monodentate taddol-derived phosphoramidite ligand,
catalytic enantiotopic-group-selective cross-couplings of achiral geminal
bis(pinacolboronates) provide a route for the construction of nonracemic chiral
organoboronates with high levels of asymmetric induction. Mechanistic
experiments suggest that the reaction occurs by a stereochemistry-determining
transmetalation with inversion of configuration at carbon.
C. Sun, B. Potter, J. P. Morken, J. Am. Chem. Soc., 2014,
136, 6534-6537.
A visible-light-induced, nickel-catalyzed, chemoselective cross-coupling
reaction between gem-borazirconocene alkanes and diverse aryl halides
provides a wide range of alkyl Bpin derivatives in high yields with excellent
regioselectivity. This practical method features attractively simple reaction
conditions and a broad substrate scope.
C. Yang, Y. Gao, S. Bai, C. Jiang, X. Qi, J. Am. Chem. Soc.,
2020, 142, 11506-11513.
A reductive three-component coupling of terminal alkynes, aryl halides,
and pinacolborane provides benzylic alkyl boronates in good yields via a hydrofunctionalization of both
π-bonds of the alkyne promoted by cooperative action of the catalysts. The
reaction offers excellent substrate scope and tolerates the presence
of esters, nitriles, alkyl halides, epoxides, acetals and alkenes.
M. K. Armstrong, G. Lalic, J. Am. Chem. Soc.,
2019,
141, 6173-6179.
A Ni-catalyzed arylboration converts substituted alkenes, aryl bromides, and
diboron reagents to products that contain a tertiary or quaternary carbon and a
synthetically versatile carbon-boron bond with control of stereoselectivity and
regioselectivity. In addition, the method is useful for the
synthesis of saturated nitrogen heterocycles.
S. R. Sardini, A. L. Lambright, G. L. Trammel, H. M. Omer, P. Liu, M. K.
Brown, J. Am. Chem. Soc.,
2019,
141, 9391-9400.
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. Int. Ed., 2002,
41, 4056-4059.
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.
A combination of nickel(II) acetylacetonate and (Z)-3,3-dimethyl-1,2-bis(diphenylphosphino)but-1-ene
catalyzes cross-coupling reactions of alkyl aryl sulfides and alkenyl alkyl
sulfides with primary and secondary alkyl Grignard reagents.
S. Kanemura, A. Kondoh, H. Yorimitsu, K. Oshima, Synthesis, 2008,
2659-2660.
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.
Aryl bromides (4 eq.) were coupled efficiently with organotin (1 eq.) using the
tetra(triphenylphosphine)palladium/polyethylene glycol 400 catalytic system in
the presence of sodium acetate as base at 100°C, providing excellent yields of
the corresponding substituted aryls in short reaction times.
H. Huang, H. Jiang, K. Chen, H. Liu, J. Org. Chem., 2009,
74, 5599-5602.
A readily available nickel/bis(oxazoline) catalyst effectively distinguishes
between a CF3 and an alkyl group and accomplishes a wide array of
enantioconvergent cross-couplings of arylzinc reagents with CF3-substituted
racemic secondary alkyl halides. This method can also be applied without
modification to the asymmetric synthesis of other families of fluorinated
organic compounds.
Y. Liang, G. C. Fu, J. Am. Chem. Soc., 2015,
137, 9523-9526.
A nickel-catalyzed cross-coupling between arylboronic acids and unactived
1-fluoro-1-iodoalkanes offers high efficiency, mild conditions, and excellent
functional-group compatibility. Readily available nitrogen and phosphine ligands
generated a variety of easily tunable catalysts to promote the fluoroalkylation
for a broad range of both coupling partners.
J. Sheng, H.-Q. Ni, G. Liu, Y. Li, X.-S. Wang, Org. Lett.,
2017, 19, 4440-4443.
Microscale parallel experimentation was used to discover catalyst systems
capable of coupling secondary organotrifluoroborates with aryl chlorides and
bromides. A ligand-dependent β-hydride elimination/reinsertion mechanism was
implicated in the cross-coupling of more hindered substrates, leading to
isomeric mixtures of coupled products in some cases.
S. D. Dreher, P. G. Dormer, D. L. Sandrock, G. A. Molander, J. Am. Chem. Soc., 2008,
130, 9257-9259.
Suitable conditions enable the Suzuki-Miyaura coupling reaction of potassium
cyclopropyl- and cyclobutyltrifluoroborates in moderate to excellent yield with
electron-rich, electron-poor, and hindered aryl chlorides to give various
substituted aryl cyclopropanes and cyclobutanes.
G. A. Molander, P. E. Gormisky, J. Org. Chem., 2008,
73, 7481-7485.
G. A. Molander, P. E. Gormisky, J. Org. Chem., 2008,
73, 7481-7485.
The palladium-catalyzed cross-coupling reaction of tricyclopropylbismuth with
aryl and heterocyclic halides and triflates tolerates numerous functional groups
and does not require anhydrous conditions. The method was successfully extended
to the cross-coupling of triethylbismuth.
A. Gagnon, M. Duplessis, P. Alsabeh, F. Barabé, J. Org. Chem., 2008,
73, 3452-3459.
A Simmon-Smith reaction of alkenyl 1,2-bis(boronates) enables the
stereodefined synthesis of cyclopropyl-1,2-bis(boronates). Subsequent
regioselective Suzuki-Miyaura couplings provide diversely tri- or
tetra-substituted arylcyclopropanes in good yields.
M. Mali, G. V. M. Sharma, S. Ghosh, T. Roisnel, B. Carboni, F. Berrée, J. Org. Chem., 2022, 87,
7649-7657.
Using commercially available Ph3PAuCl and readily prepared, benign
arylsilanes, a gold-catalyzed oxyarylation of alkenes proceeds smoothly in air.
The oxidant, Selectfluor, not only facilitates entry to the Au(I/III) manifold
but also provides a fluoride anion for silane activation, thereby avoiding the
need for addition of a stoichiometric base.
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dehydrative C-H alkenylation and annulation reaction. The catalytic C–H coupling
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liberates water as the only byproduct.
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reaction partners. The concise formation of a variety of building blocks,
such as those described here, has found wide applicability in our drug
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a vinyl halide, and a vinyl triflate to epoxides under reducing conditions. For
terminal epoxides, the regioselectivity of the reaction depends upon the
cocatalyst employed. Iodide cocatalysis results in opening at the less hindered
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γ-aryl carboxylic acids. Both internal and terminal alkenes
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range of functional groups and substitution patterns, thus constituting a
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functionalized arylated carbonyl products, with excellent enantioselectivity
under mild conditions, bearing a range of useful functionality. The
regioselectivity of the initial migratory insertion depends on the electronic
nature of the boronic acid.
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provides alkyl-substituted aromatic rings
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cross-coupling reactions are promoted by simple Cu-based catalysts and do not
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olefin (EDO) ligand. Under optimized conditions, a wide range of amides derived
from 3-butenoic acid, 4-pentenoic acid, and allyl amines are compatible
substrates.
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reactive, dicationic species is reported.
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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.
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A unique
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hydrogen atoms in a mild, modular, and practical direct hydroarylation of vinyl amine
derivatives with a wide range of aryl halides (including aryl chlorides). This
general and highly chemoselective protocol delivers a broad range of
arylethylamine products with complete regiocontrol.
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construct a tertiary stereogenic center.
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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.
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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%.
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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.
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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.
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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.
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The use of a H8-BINOL-based phosphoramidite ligand enables a
Pd-catalyzed highly enantioselective three-component coupling of 1,3-dienes with
aryl iodines and sodium dialkyl malonates via a Pd-catalyzed cascade arylation
and asymmetric allylic alkylation reaction. This reaction provides an efficient
strategy for the enantioselective 1,2-difunctionalization of 1,3-dienes.
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The use of an equimolar amount of base with a diborylmethane enabled a
chemoselective Pd-catalyzed Suzuki–Miyaura cross-coupling reaction for the
synthesis of various benzylboronate derivatives in very good yields. Reactions
of sterically hindered aryl bromides can give products in good yields.
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Catalytic enantioselective conjunctive cross-couplings that employ Grignard
reagents provide chiral organoboronic esters in an efficient and highly
selective fashion. The use of sodium triflate enables "ate" complex formation
and overcomes catalytic inhibition by halide ions.
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An efficient synthesis of 9H-fluorene derivatives through a
Pd(0)-catalyzed cross-coupling reaction of 1,1-diboronates with 2,2′-dibromobiphenyls
offers high yields, operational simplicity, and mild reaction conditions.
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