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Synthesis of allylic amines

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Iridium catalysts derived from a phosphoramidite containing a biphenolate group, one distal chiral substituent at nitrogen and a large achiral cycloalkyl group were shown to react in all cases examined with nearly the same rates, regioselectivities, and enantioselectivities as catalysts derived from the previously reported, more elaborate ligands.
A. Leitner, S. Shekhar, M. J. Pouy, J. F. Hartwig, J. Am. Chem. Soc., 2005, 127, 15506-15514.

Palladium-catalyzed isomerization of readily accessible racemic, branched aromatic allylic esters to terminal allylic esters, followed by sequential iridium-catalyzed allylic substitution, gave branched allylic amines, ethers, and alkyls in good yield with high regioisomeric and enantiomeric selectivity.
S. Shekhar, B. Trantow, A. Leitner, J. F. Hartwig, J. Am. Chem. Soc., 2006, 128, 11770-11771.

The allylic amination and etherification of a broad range of allylic carbonates occurred in high yields and with high regioselectivities and enantioselectivities with an activated metallacyclic iridium catalyst containing a bis-naphthethylamino group.
A. Leitner, C. Shu, J. F. Hartwig, Org. Lett., 2005, 7, 1093-1096.

An iridium-catalyzed enantioselective allylic amination of (E)-cinnamyl and terminal aliphatic allylic carbonates using chiral phosphoramidites as ligands provided branched secondary and tertiary allylic amines in high yields with excellent regio- and enantioselectivity. Reactions in THF displayed the most suitable balance of rate and enantioselectivity.
T. Ohmura, J. F. Hartwig, J. Am. Chem. Soc., 2002, 124, 15164-15165.

KF-Celite is an efficient, inexpensive, noncorrosive, and environmentally friendly catalyst for the allylation of anilines. By using only a 1/1.2 stoichiometric ratio of electrophilic reagent to aniline, monoallylated products are obtained in high isolated yields in very short reaction times.
V. Pace, F. Martínez, M. Fernández, J. V. Sinisterra, A. R. Alcántara, Org. Lett., 2007, 9, 2661-2664.

A Pd-catalysed termolecular allenylation cascade followed by a Ru catalysed RCM process affords a diverse range of Δ³-aryl/heteroaryl substituted five-seven membered nitrogen and oxygen heterocycles.
H. A. Dondas, B. Clique, B. Cetinkaya, R. Grigg, C. Kilner, J. Morris, V. Sridharan, Tetrahedron, 2005, 61, 10652-10666.

Various allyl carbonates have been converted under Fe catalysis into essentially regio- and stereoisomerically pure allyl amines. Catalytic amounts of piperidinium hydrochloride as a buffer retard catalyst decomposition.
B. Plietker, Angew. Chem. Int. Ed., 2006, 45, 6053-6056.

COP-Cl catalyzes the rearrangement of (E)-allylic trichloroacetimidates to provide transposed allylic trichloroacetamides of high enantiopurity. This practical method for transforming prochiral allylic alcohols to enantioenriched allylic amines offers high functional group compatibility.
C. E. Anderson, L. E. Overman, J. Am. Chem. Soc., 2003, 125, 12412-12413.

Privileged allylic amine structures can be constructed in a regioselective, stereoselective, and diversity-oriented manner by a novel palladium-catalyzed four-component assembly based on allenylboronate platform. A short synthesis of rolipram is also demonstrated.
K. Tonogaki, K. Itami, J.-I. Yoshida, J. Am. Chem. Soc., 2006, 128, 1464-1465.

The synthesis and properties of different planar chiral 1-phosphino-2-sulfenylferrocene ligands are reported. Very high enantioselectivities were obtained in the palladium-catalyzed allylic substitution of 1,3-diphenyl-2-propenyl acetate with dimethyl malonate and nitrogen nucleophiles using readily available tert-butylsulfenyl derivatives.
O. G. Mancheno, J. Priego, S. Cabrera, R. G. Arrayas, T. Llamas, J. C. Carretero, J. Org. Chem., 2003, 68, 3679-3686.

A mild, gold(I)-catalyzed hydroamination of 1,3-dienes is reported. Various carbamates and sulfonamides add to conjugated dienes to affort protected allylic amines in good to high yields.
C. Brouwer, C. He, Angew. Chem. Int. Ed., 2006, 45, 1744-1747.

Bi(OTf)₃/Cu(CH₃CN)₄PF₆ efficiently catalyzes an intermolecular 1:1 hydroamination of 1,3-dienes with various carbamates, sulfonamides, and carboxamides to afford allylic amines in good yield.
H. Qin, N. Yamagiwa, S. Matsunaga, M. Shibasaki, J. Am. Chem. Soc., 2006, 128, 1611-1614.

A highly enantioselective and catalytic vinylation of aldehydes leads to allylic alcohols that are then transformed to the allylic amines via Overman's [3,3]-sigmatropic rearrangement of imidates. Oxidative cleavage of the allylic amines furnishes amino acids in good yields and excellent ee's. The scope and utility of this method are demonstrated by the synthesis of challenging allylic amines and their subsequent transformation to valuable nonproteinogenic amino acids, including both D and L configured (1-adamantyl)glycine.
Y. K. Chen. A. E. Lurain, P. J. Walsh, J. Am. Chem. Soc., 2002, 124, 12225-12231.

3-Pyrroline has been prepared from (Z)-1,4-dichloro-2-butene in three steps in an overall yield of 74%. The Delépine Reaction permitted the monoamination of the substrate in practically quantitative yields. The subsequent ring-closing reaction was less efficient.
S. Brandänge, B. Rodriquez, Synthesis, 1988, 347-348.

The synthesis of isomerically pure allylic amines, including farnesyl amine, is achieved in excellent yields using a modified Gabriel synthesis.
S. E. Sen, S. L. Roach, Synthesis, 1995, 756-758.