Categories: Synthesis of N-Heterocycles > Synthesis of cyclic amines >
Synthesis of piperidines
Recent Literature
A new efficient method for the N-heterocyclization of primary amines
with diols catalyzed by a Cp*Ir complex was developed. A variety of five-,
six-, and seven-membered cyclic amines were synthesized in good to excellent
yields.
K.-I. Fujita, T. Fujii, R. Yamaguchi, Org. Lett., 2004, 6,
3525-3528.
A one-pot synthesis of nitrogen-containing heterocycles from alkyl dihalides
and primary amines and hydrazines occurs under microwave irradiation via a
simple and efficient cyclocondensation in an alkaline aqueous medium.
Y. Ju, R. S. Varma, J. Org. Chem., 2006, 71, 135-141.
An asymmetric intramolecular hydroamination of allenes catalyzed by
phosphinegold(I)-bis-p-nitrobenzoate complexes is applicable to the
enantioselective formation of vinyl pyrrolidines and piperidines in high ee.
R. L. LaLonde, B. D. Sherry, E. J. Kang, F. D. Toste, J. Am. Chem. Soc., 2007,
129, 2452-2453.
Optically pure C2-symmetrical cyclic amines were
efficiently synthesized from the corresponding diols obtained from an
enantioselective borohydride reduction of diketones in the presence of a chiral
β-ketoiminato cobalt(II) catalyst.
M. Sato, Y. Gunji, T. Ikeno, T. Yamada, Synthesis, 2004,
1434-1438.
Iodocyclization of unsaturated tosylamides promoted by Oxone oxidation of KI
afforded, in good yields, N-tosyl iodopyrrolidines and piperidines. A
new, simple method for the conversion of alcohols to tosylamides is
presented.
M. C. Marcotullio, V. Campagna, S. Sternativo, F. Costantino, M. Curini, Synthesis, 2006, 2760-2766.
A mild, effective gold(I)-catalyzed hydroamination of unactivated olefins to
form protected nitrogen heterocycles has been developed. The substrate scope
is broader than in reactions realized with late-transition-metal catalyst
systems.
X. Han, R. A. Widenhoefer, Angew. Chem. Int. Ed., 2006, 45, 1747-1749.
Treatment of an N-4-pentenyl or N-5-hexenyl urea with a
catalytic 1:1 mixture of a gold(I) N,N-diaryl imidazol-2-ylidine complex and
AgOTf gave the corresponding nitrogen heterocycle in excellent yield via an
intramolecular exo-hydroamination.
C. F. Bender, R. A. Widenhoefer, Org. Lett., 2006, 8, 5303-5305.
A mild and facile Pd-catalyzed intramolecular hydroamination of unactivated
alkenes takes place at room temperature and tolerates acid-sensitive functional
groups. The tridentate ligand on Pd effectively inhibits β-hydride elimination, thus
the formation of hydroamination products is preferred over oxidative amination
products.
F. E. Michael, B. M. Cochran, J. Am. Chem. Soc.,
2006, 128, 4246-4247.
Hoveyda-Grubbs catalyst in combination with BF3·OEt2 efficiently promotes
tandem cross metathesis intramolecular aza-Michael reaction between enones and
unsaturated carbamates resulting in the creation of β-amino carbonyl units. The
use of microwave irradiation dramatically accelerates the process, but also inverts the
stereoselectivity in the addition process.
S. Fustero, D. Jiménez, M. Sánchez-Roselló, C. del Pozo, J. Am. Chem. Soc., 2007,
129, 6700-6701.
The Au(I)-catalyzed intramolecular hydroamination of N-allenyl
carbamates was effective for the formation of various cyclic amines. γ-Hydroxy
and δ-hydroxy allenes underwent Au-catalyzed intramolecular
hydroalkoxylation to form the corresponding
oxygen heterocycles in good yield. 2-Allenyl indoles
underwent Au-catalyzed intramolecular hydroarylation to form 4-vinyl tetrahydrocarbazoles in good yield.
Z. Zhang, C. Liu, R. E. Kinder, X. Han, H. Qian, R. A. Widenhoefer, J. Am. Chem. Soc.,
2006, 128, 9066-9073.
tert-Butyl hypoiodite is a mild and powerful reagent for the
cyclization of N-alkenylamides leading to various N-heterocycles.
N-alkenylsulfonamides gave three- to six-membered saturated N-heterocycles
in good yields, whereas alkenylbenzamide derivatives afforded
N-, O- or N-, S-heterocycles.
S. Minakata, Y. Morino, Y. Oderaotoshi, M. Komatsu, Org. Lett.,
2006, 8, 3335-3337.
An intramolecular anti-Markovnikov hydroamination of
1-(3-aminopropyl)vinylarenes occurred in the presence of [Rh(COD)(DPPB)]BF4
as catalyst to form 3-arylpiperidines in high yield. Reactants with substituents
β to the amino group formed 3,5-disubstituted piperidines with high
diastereomeric excess, whereas substituents in α and γ gave mostly enamines and
isomerized starting materials.
A. Takemiya, J. F. Hartwig, J. Am. Chem. Soc.,
2006, 128, 6042-6043.
A novel approach to 2,4-disubstituted piperidines involves the radical
cyclization of 7-substituted-6-aza-8-bromooct-2-enoates. An enhancement in
diastereoselectivity using tris(trimethylsilyl)silane instead of tributyltin
hydride is discussed.
L. A. Gandon, A. G. Russel, T. Güveli, A. E. Brodwolf, B. M. Kariuki, N.
Spencer, J. S. Snaith, J. Org. Chem., 2006, 71, 5198-5207.
An intramolecular iodo-aldol cyclization of prochiral α-substituted enoate
aldehydes and ketones produces hetero- and carbocycles containing quaternary centers adjacent
to secondary or tertiary centers. The reactions occur in good yields and are
highly trans-selective with hydroxyl and iodomethyl
groups on opposite faces of the ring system.
F. Douelle, A. S. Capes, M. F. Greaney, Org. Lett., 2007,
9, 1931-1934.
An efficient method to activate hydroxyl groups of amino alcohols has been
developed, which avoids the use of toxic reagents and tolerates various
functional groups. This strategy has been applied to the synthesis of
functionalized p-methoxyphenyl-protected azetidines, pyrrolidines,
and piperidines.
R. M. de Figueiredo, R. Fröhlich, M. Christmann, J. Org. Chem., 2006, 71, 4147-4154.
A mild, complete hydrogenation of aromatic rings catalyzed by heterogeneous 10%
Rh/C proceeds at 80 °C in water under 5 atm of H2 pressure and is
applicable to the hydrogenation of various carbon and heteroaromatic compounds
such as alkylbenzenes, biphenyls, pyridines and furans.
Maegawa, A. Akashi, H. Sajiki, Synlett,
2006, 1440-1442.
