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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 simple, one-pot preparation of cyclic amines via efficient chlorination of amino alcohols with use of SOCl₂ obviates the need for the classical N-protection/O-activation/cyclization/deprotection sequence commonly employed for this type of transformation. The reaction pathways and the general scope of this method have also been investigated.
F. Xu, B. Simmons, R. A. Reamer, E. Corley, J. Murry, D. Tschaen, J. Org. Chem., 2008, 73, 312-315.

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.

Mild, rhodium-catalyzed hydroaminations of unactivated olefins with primary and secondary alkylamines form the corresponding five- and six-membered products in excellent yields. A variety of functional groups such as hydroxyl, halo, cyano, and carboalkoxyl groups were tolerated.
Z. Liu, J. F. Hartwig, J. Am. Chem. Soc., 2008, 130, 1570-1571.

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 highly enantioselective rearrangement of β-amino alcohols was realized by using a catalytic amount of trifluoroacetic anhydride.
T.-X. Métro, D. G. Pardo, J. Cossy, J. Org. Chem., 2007, 72, 6556-6561.

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.