Categories: C-N Bond Formation > Amines >
Synthesis of propargylic amines
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A copper(I) complex of i-Pr-pybox-diPh efficiently catalyzes the
enantioselective one-pot three-component synthesis of propargylamines from
aromatic aldehydes, anilines, and alkynes. A transition-state model has been
proposed.
A. Bisai, V. K. Singh, Org. Lett.,
2006,
8, 2405-2408.
A wide range of chiral
propargylamines can be prepared in a one-pot three-component reaction
between an alkyne, an aldehyde and a secondary amine at room temperature in
the presence of CuBr and (R)-quinap in good yield and good
enantioselectivity.
N. Gommermann, C. Koradin, K. Polborn, P. Knochel, Angew.
Chem., 2003, 115, 5941-5944.
A metal-free decarboxylative three-component coupling reaction was developed.
When alkynyl carboxylic acids, paraformaldehyde, and amines were reacted in
CH3CN at 65 °C for 3 h, the desired propargylamines were obtained in good yields.
This coupling reaction also showed good yield in water solvent. This reaction
showed higher selectivity toward alkynyl carboxylic acids than a terminal alkyne.
K. Park, Y. Heo, S. Lee, Org. Lett., 2013,
15, 3322-3325.
A copper-based system enables methylene insertion between an amine and an
alkyne counterpart, via C-N bond cleavage of N,N-dimethylacetamide. The
method gives an expedient access to a broad range of propargylic amines in good
yields.
A. Rahaman, R. D. Shinde, S. Bhadra, J. Org. Chem., 2023, 88,
1884-1889.
A single Cu(II) catalyst couples a diverse range of nitrogen sources with
various alkynes and aldehydes without the addition of ligand or base.
Copper-catalyzed alkynylation involving p-toluenesulfonamide provides
high yields of N-Ts-protected propargylamines. The superior activity of
copper(II) triflate also allows this three-component alkynylation to incorporate
a ketone.
C. E. Meyet, C. J. Pierce, C. H. Larsen, Org. Lett., 2012,
14, 964-967.
An economic and practical transformation from secondary alkyl-substituted
propargyl acetates to a variety of nucleophilic substitution products is
catalyzed by inexpensive InCl3. High yields and excellent
chemoselectivity were obtained. Five-, six-, and seven-membered propargyl
cycloethers were also successfully constructed.
M. Lin, L. Hao, X.-t. Liu, Q.-z. Chen, F. Wu, P. Yan, S.-x. Xu, X.-l. Chen, J.-j.
Wen, Z.-p. Zhan, Synlett, 2011,
665-670.
Microwave-assisted conditions enabled a simple, rapid, one-pot synthesis of
arylaminomethyl acetylenes in very good yields using arylboronic acids, aqueous
ammonia, propargyl halides, copper(I) oxide and water as the solvent within ten
minutes.
Y. Jiang, S. Huang, Synlett, 2014, 25,
407-410.
A nickel-catalyzed asymmetric propargylic amination of
propargylic carbonates bearing an internal alkyne group with N-methylaniline derivatives provides the corresponding chiral
propargylic amines in very good yields with excellent enatioselectivities.
K. Watanabe, Y. Miyazaki, M. Okubo, B. Zhou, H. Tsuji, M. Kawatsaru, Org. Lett.,
2018, 20, 5448-5451.
A BF3-mediated in situ generation of alkynyl imines followed by
alkynylation or allylation with boronic esters enables an efficient synthesis of
α-alkynyl- or α-allyl-substituted N-Boc-propargylic amines in good yields
under mild conditions.
K. Yasumoto, T. Kano, K. Maruoka,
Org. Lett., 2019, 21, 3214-3217.
A simple Re2O7-catalyzed direct dehydrative coupling
between π-activated alcohols with electron-deficient amines has been
achieved under mild and open flask conditions. The protocol alows the conversion
of allylic, benzylic, and propargylic alcohols. The mechanistic proof for the SN1-type
process has also been provided.
B. G. Das, R. Nallagonda, P. Ghorai, J. Org. Chem., 2012,
77, 5577-5583.
An oxidative amination of allenes using a single hypervalent iodine reagent
proceeds very efficiently for monosubstituted allenes and leads to formation of
the corresponding propargylic amines, either as the internal or as the terminal
amine depending on the addition of triphenylphosphine oxide to the iodine(III)
reagent.
N. Purkait, S. Okumura, J. A. Souto, K. Muņiz, Org. Lett.,
2014,
16, 4750-4753.
A one-pot catalyst-free chemoselective synthesis of N-benzyl
propargylamines with good functional group compatibility involves in situ
formation of an active amine through Petasis reaction of primary amines,
formaldehyde solution, and boronic acids, which reacts in a decarboxylative
coupling reaction with propiolic acids to give products in high yields.
H. Feng, H. Jia, Z. Sun, J. Org. Chem.,
2014,
79, 11812-11818.
A highly enantioselective, catalytic three-component coupling of aldehydes,
alkynes, and 4-piperidone hydrochloride hydrate affords the corresponding
tertiary propargylamines in useful yields. A selective cleavage of the
piperidone protecting group is possible using either ammonia/EtOH or a
polymer-supported scavenger amine.
P. Aschwanden, C. R. J. Stephenson, E. M. Carreira, Org. Lett.,
2006,
8, 2437-2440.
A highly efficient gold-catalyzed three-component-coupling of aldehydes,
alkynes, and amines in water was developed. Excellent yields of the
corresponding propargylamines were obtained in most cases for both aromatic
and aliphatic aldehydes and various amines.
C. Wei, C.-J. Li, J. Am. Chem. Soc., 2003,
125, 9584-9585.
A three-component coupling between an aldehyde, alkyne and amine is
catalyzed by silver iodide to generate propargylic amines in high yields in
water without cocatalyst or activator. This method is especially effective for
reactions involving aliphatic aldehydes.
C. Wei, Z. Li, C.-J. Li, Org. Lett., 2003,
5, 4473-4475.
A three-component coupling reaction of alkynylsilanes, aldehydes and amines
produces a variety of propargyl amine derivatives by a cooperative catalytic
system comprised of CuCl and Cu(OTf)2. This catalytic system was
successfully applied to the practical preparation of 1,6-diyne derivatives
via twice-performed, domino-type coupling reactions.
N. Sakai, N. Uchida, T. Konakahara, Synlett, 2008,
1515-1519.
A highly efficient microwave-assisted Cu(I)-catalyzed
cross-A3-coupling/decarboxylative coupling of two different amines, formaldehyde,
and propiolic acid provides unsymmetric 1,4-diamino-2-butynes through a domino
process in good yields with high chemoselectivity.
X. Xu, H. Feng, E. V. Van der Eycken, J. Org. Chem., 2021, 86,
14036-14043.
A Cu-catalyzed propargylic amination of amines with propargylic cyclic
carbonates provides chiral acyclic α-quaternary α-amino ketones. This protocol
offers wide functional group tolerance and high asymmetric induction.
W. Guo, L., Zuo, M. Cui, B. Yan, S. Ni, J. Am. Chem. Soc.,
2021, 143, 7629-7634.
Propargylamines have been synthesized by a gold(III) salen complex-catalyzed
three-component coupling reaction of aldehydes, amines, and alkynes in water
in excellent yields at 40°C. With chiral prolinol derivatives as the amine
component, excellent diastereoselectivities have been attained.
V. K.-Y. Lo, Y. Liu, M.-K. Wong, C.-M. Che, Org. Lett.,
2006,
8, 1529-1532.
L. Zani, S. Alesi, P. G. Cozzi, C. Bolm, J. Org. Chem.,
2006,
71, 1558-1562.
A general and efficient FeCl3-catalyzed substitution reaction of
propargylic alcohols with carbon- and heteroatom-centered nucleophiles such
as allyl trimethylsilane, alcohols, aromatic compounds, thiols, and amides,
forms new C-C, C-O, C-S and C-N bonds.
Z.-P. Zhan, J.-L. Yu, Y.-Y. Cui, R.-F. Yang, W.-Z. Yang, J.-P. Li, J. Org. Chem., 2006,
71, 8298-8301.
A boryl-directed intermolecular C-H amination of allyl N-methyliminodiacetyl
boronates (B(MIDA)s) and propargylic B(MIDA)s provide α-amino boronates with an
exceptionally high level of site-selectivity. A wide variety of highly
functionalized secondary and tertiary α-amino boronates are formed in very good
yields under mild reaction conditions.
Y. Liu, Z.-H. Chen, Y. Li, J. Qian, Q. Li, H. Wang, J. Am. Chem. Soc.,
2022, 144, 14380-14387.