Categories: C-C Bond Formation > Amines, Arenes >
Synthesis of benzylamines
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Recent Literature
A Mannich-like zinc-mediated three-component reaction of aromatic halides,
amines, and paraformaldehyde allows the straightforward synthesis of a range of
functionalized tertiary benzylamines. This procedure involves the in situ
formation of arylzinc reagents.
E. Le Gall, A. Decompte, T. Martens, M. Troupel, Synthesis, 2010,
249-254.
Suzuki-Miyaura cross-coupling reactions of Boc-protected
aminomethyltrifluoroborate with a variety of both aryl and hetaryl chlorides
gives aminomethylated arenes in very good yields. Potassium Boc-protected
aminomethyltrifluoroborate can successfully be synthesized through a
one-pot process.
G. A. Molander, I. Shin, Org. Lett., 2011,
13, 3956-3959.
Suzuki-Miyaura cross-coupling enables a one-pot primary aminomethylation of aryl
halides, triflates, mesylates, and tosylates via coupling with sodium
phthalimidomethyltrifluoroborate followed by deamidation with ethylenediamine.
N. Murai, M. Miyano, M. Yonaga, K. Tanaka, Org. Lett., 2012,
14, 2818-2821.
Scope and limitations of the Suzuki-Miyaura reaction of N,N-dialkylaminomethyltrifluoroborates
with aryl halides were investigated. Aryl chlorides, iodides, and triflates
coupled in good to excellent yields to give N,N-dialkylbenzylic amines.
G. A. Molander, P. E. Gormisky, D. L. Sandrock, J. Org. Chem., 2008,
73, 2052-2057.
The combination of chiral bicyclo[3.3.0]octadiene ligands, an active rhodium
hydroxide complex, and neutral reaction conditions enabled a highly
enantioselective rhodium-catalyzed arylation of aliphatic N-tosylaldimines
in high yield. The application of this method is demonstrated by the
enantioselective synthesis of chiral 2-aryl pyrrolidines and piperidines in a
one-pot procedure.
Z. Cui, H.-J. Yu, F.-F. Yang, W.-Y. Gao, C.-G. Feng, G.-Q. Lin, J. Am. Chem. Soc., 2011,
133, 12394-12397.
The synthesis of free α-chiral amines by a one-pot multicomponent procedure
involves the formation of N-diphenylphosphinoylimines from
commercially available starting materials and the subsequent
enantioselective addition of diakylzinc reagents using an air-stable
precatalyst complex.
A. Cote, A. B. Charette, J. Org. Chem.,
2005,
70, 10864-10867.
An asymmetric arylation of N-tosylimines with arylboronic acids was
realized by using a chiral cationic C2-symmetric N-heterocyclic
carbene Pd2+ diaquo complex as catalyst in combination with K3PO4
• 3 H2O in THF at 4°C in the presence of powdered 4 Å MS to afford
the corresponding adducts in excellent yields and good enantioselectivities.
G.-N. Ma, T. Zhang, M. Shi, Org. Lett., 2009,
11, 875-878.
A nickel/photoredox dual catalysis strategy enables a site-selective
α-arylation of various trialkylamines with exclusive N-Me selectivity
under mild conditions, even in the context of late-stage arylation of pharmaceutical compounds bearing this common structural motif.
Y. Shen, T. Rovis, J. Am. Chem. Soc.,
2021, 143, 16364-16369.
A nickel-catalyzed asymmetric decarboxyarylation of NHP esters via reductive
cross-coupling provides structurally diverse chiral benzylamines. This method
has demonstrated excellent catalytic efficiency, high enantioselective control,
mild conditions, and good functional group tolerance.
C.-Y. Wang, Y.-L. Huang, W.-C. Xu, G. Gao, P. Liu, Y.-X. Bi, G.-K. Liu, X.-S.
Wang, Org. Lett., 2023, 25,
6925-6930.
ert-Butylperoxyamido acetals can be generated in high yields under
mild conditions via oxidative functionalization of C-H bonds adjacent to the amide nitrogen atom. Treatment with Grignard reagents enables the synthesis of
α-substituted amides.
H. Yu, J. Shen, Org. Lett., 2014,
16, 3204-3207.
A highly efficient Bi(OTf)3-catalyzed multicomponent synthesis of
amidomethylated arenes and heteroarenes from readily available starting
materials proceeds under mild conditions and has a broad substrate scope with
water as the only side product.
A. E. Schneider, G. Manolikakes, Synlett, 2013, 24,
2057-2060.
A copper-catalyzed Petasis-type reaction of imines, acid chlorides, and
organoboranes gives α-substituted amides. This reaction does not require the use
of activated imines or the transfer of special units from the organoboranes and
represent a useful generalization of the Petasis reaction.
M. S. T. Morin, Y. Lu, D. A. Black, B. A. Arndtsen, J. Org. Chem., 2012,
77, 2013-2017.
A highly efficient three-component coupling reaction between thioformamides and
organolithium and Grignard reagents was developed. The generality of the process
has been demonstrated by using various combinations of reactants and reagents.
T. Murai, F. Asai, J. Am. Chem. Soc., 2007,
129, 780-781.
A highly efficient asymmetric intermolecular Ni-catalyzed reductive
dicarbofunctionalization of vinyl amides, vinyl boranes, or vinyl phosphonates
with two distinct readily available electrophiles, namely, Csp2- and
Csp3-halides, provides chiral products in a highly regio- and
enantioselective manner.
X. Wei, W. Shu, A. García-Domínguez, E. Merino, C. Nevado, J. Am. Chem. Soc.,
2020, 142, 13515-13522.
Sequential addition reactions of Grignard reagents to thioformamides give
tertiary amines in an efficient manner. The addition of different Grignard
reagents can be accomplished by using one equivalent of arylmagnesium reagent in
the first step followed by alkyl, alkenyl, aryl, or alkynyl reagents to afford
the corresponding amines in good to high yields.
T. Murai, K. Ui, Narengerile, J. Org. Chem., 2009,
74, 5703-5706.
A general aminoalkylation of aryl halides with α-silylamines overcomes
intolerance of free amines in nickel-mediated C-C coupling. The reaction
features broad functional group tolerance and high efficiency. The fast
desilylation is facilitated by single-electron transfer (SET) in the presence of
carbonate to provide α-amino radicals, which then engage in nickel-mediated C-C
coupling.
W. Dong, S. O. Badir, X. Zhang, G. A. Molander, Org. Lett., 2021, 23,
4250-4255.
A mild, versatile, copper-catalyzed three-component coupling of organoindium
reagents with imines and acid chlorides provides α-substituted amides
or N-protected amines in a single step with the sole byproduct being
indium trichloride.
D. A. Black, B. A. Arndtsen, Org. Lett.,
2006,
8, 1991-1993.
Highly regioselective and efficient Heck reactions of aryl triflates with N-acyl-N-vinylamines
were achieved using Pd2(dba)3, dppf, and diethylisopropylamine in dioxane. The coupling products easily
underwent acidic hydrolysis to the corresponding aryl methyl ketones or in situ
hydrogenation in the presence of (Ph3P)3RhCl under a
hydrogen atmosphere to provide the N-acyl derivatives of benzylic amines.
A. L. Hansen, T. Skydstrup, J. Org. Chem., 2005,
70, 5997-6003.
A nickel-catalyzed reductive cross-coupling of cyclopropylamine NHP esters
with (hetero)aryl halides provides direct access to 1-arylcyclopropylamines, a
bioisosteric motif commonly used in small molecule drug discovery. The reaction
proceeds rapidly (<2 h) with excellent functional group tolerance. The method
can also be extended to the arylation of four-membered strained rings.
M. S. West, A. L. Gabbey, M. P. Huestis, S. A. L. Rousseaux, Org. Lett., 2022, 24,
8441-8446.