Categories: C-N Bond Formation > Amines >
Synthesis of α-Amino ketones, acids, esters, nitriles and related compounds
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Use of cinchona ligands with an anthraquinone (AQN) core, in place of the
usual phthalazine (PHAL) core, in the asymmetric aminohydroxylation of
cinnamates causes dramatic reversal of the regioselection, so that phenyl
serines are obtained in high enantiomeric excess. Hence, the regioselectivity is
controlled by the ligand and not the substrate.
B. Tao, G. Schlingloff, K. B. Sharpless, Tetrahedron Lett., 1998,
39, 2507-2510.
A mild and efficient monocarboxymethylation of a broad range of primary amines
takes place under aqueous conditions at room temperature. Treatment of primary
amines with two equivalents of glyoxylic acid leads to N-formyl glycine
derivatives. Subsequent hydrolysis of the crude reaction solution gives
monocarboxymethylated products in very good yield.
T. J. K. Gibbs, M. Boomhoff, N. C. O. Tomkinson, Synlett, 2007,
1573-1575.
A highly efficient copper-catalyzed asymmetric insertion of α-diazoesters into
N-H bonds using chiral spiro bisoxazoline ligands affords α-amino acid derivatives in high yields with excellent
enantioselectivities.
B. Liu, S.-F. Zhu, W. Zhang, C. Chen, Q.-L. Zhou, J. Am. Chem. Soc., 2007,
129, 5834-5835.
A new Cu/chiral bipyridine catalyst for the asymmetric insertion of
α-diazocarbonyl compounds into the N-H bonds of carbamates generate an array of
easily deprotected arylglycines in good ee.
E. C. Lee, G. C. Fu, J. Am. Chem. Soc.,
2007,
129, 12066-12067.
D. F. Taber, R. B. Sheth, P. V. Joshi, J. Org. Chem., 2005,
70, 2851-2854.
A straightforward three-component reaction of preformed aromatic or in situ
generated benzylic organozinc reagents with amines and ethyl glyoxylate allows
the synthesis of a range of α-amino esters in very good yields. The procedure,
which is characterized by its simplicity, allows the concise synthesis of esters
bearing a phenylglycine or a phenylalanine scaffold.
C. Haurena, E. Le Gall, S. Sengmany, T. Martens, M. Troupel, J. Org. Chem., 2010,
75, 2645-2650.
C. Haurena, E. Le Gall, S. Sengmany, T. Martens, M. Troupel, J. Org. Chem., 2010,
75, 2645-2650.
A simple, commercially available iridium catalyst allows the use of sulfoxonium
ylides as a carbene source for various intra- and intermolecular X-H bond
insertions, including a practical ring-expansion strategy for lactams. The
safety and stability of sulfoxonium ylides recommend them as preferable
surrogates to traditional diazo ketones and esters.
I. K. Mangion, I. K. Nwamba, M. Shevlin, M. A. Huffman, Org. Lett., 2009,
11, 3566-3569.
The use of iodosobenzene (PhIO) as oxidant and p-toluenesulfonamide (TsNH2)
as aminating reagent in the presence of a catalytic amount of perchlorate zinc
hexahydrate enables a direct α-amination of β-dicarbonyl compounds. The reaction
proceeds quickly at rt to provide the corresponding α-N-tosylamido
β-dicarbonyl compounds very good yields.
J. Yu, S.-S. Liu, J. Cui, X.-S. Hou, C. Zhang, Org. Lett., 2012,
14, 832-835.
The intriguing Rh2(OAc)4 and chiral Brønsted acid
cocatalyzed three-component Mannich-type reaction of a diazo compound, a
carbamate, and an imine provides rapid and efficient access to both syn-
and anti-α-substituted α,β-diamino acid derivatives with a high level
control of chemo-, diastereo-, and enantioselectivity.
J. Jiang, H.-D. Xu, J.-B. Xi, B.-Y. Ren, F.-P. Lv, X. Guo, L.-Q. Jiang, Z.-Y.
Zhang, W.-H. Hu, J. Am. Chem. Soc., 2011,
133, 8428-8431.
C-Acylimines undergo intermolecular amidation with amides to produce monoacyl
gem-diamino acid derivatives in the presence of Cu(OTf)2 and PPh3
under mild conditions. This method provides an efficient access to gem-diamino
acid equivalents with good to excellent yields.
S. Zhu, J. Dong, S. Fu, H. Jiang, W. Zeng, Org. Lett., 2011,
13, 4914-4917.
Chelated amino acid ester enolates react with aromatic nitro compounds in a
1,3-addition mode at the nitro group giving amino acids bearing an
aryl(hydroxy)amino side chain. Two equivalents of enolate are necessary for
complete conversion, because one equivalent is oxidized during the reaction.
D. Stolz, U. Kazmaier, R. Pick,
Synthesis, 2006, 3341-3347.
Different aldehydes and amines react with acyl cyanides in the presence of a
catalytic amount of the Schreiner thiourea catalyst to give the corresponding N-acyl amino nitriles in high yields. The scope of the reaction is broad and
allows the use of both aromatic and aliphatic aldehydes and amines.
S. C. Pan, B. List, Synlett, 2007, 318-320.
The regio- and stereoselective aminochlorination of α,β-unsaturated ketones
with N,N-dichloro-p-toluenesulfonamide (4-TsNCl2) and
CuOTf as catalyst provides an easy access to
vicinal haloamino ketones, with excellent regioselectivity and good yields.
Aromatic and aliphatic enones give opposite regioselectivity.
D. Chen, C. Timmons, S. Chao, G. Li, Eur. J. Org. Chem., 2004,
3097-3101.
L-Proline-catalyzed asymmetric α-amination of ketones proceeds with various azodicarboxylates as the
nitrogen source in high yields and excellent enantioselectivities. The scope and potential of the reaction are demonstrated by further
transformation of the α-hydrazino ketones formed to both optically active syn and
anti-α-amino alcohol derivatives.
N. Kumaragurubaran, K. Juhl, W. Zhuang, A. Gogevig, K. A. Jorgensen, J. Am. Chem. Soc., 2002,
124, 6254-6255.
Chiral tertiary α-hydroxy esters were transformed to α-azido esters by Mitsunobu
reaction with HN3. Reactions proceed at room temperature with high
chemical yield using 1,1-(azodicarbonyl)dipiperidine (ADDP) and
trimethylphosphine (PMe3) with complete inversion of configuration at
the α-carbon. Several α,α-disubstituted amino acids were synthesized in high
overall chemical yield and optical purity.
J. E. Green, D. M. Bender, S. Jackson, M. J. O'Donnell, J. R. McCarthy, Org. Lett., 2009,
11, 807-810.
A novel enantioselective synthesis of α-amino acids has been developed,
which is broad in scope, simple in application, and advantageous for many α-amino acids
of interest in chemistry, biology, medicine.
E. J. Corey, J. O. Link, J. Am. Chem. Soc., 1992,
114, 1906-1908.
Related
N-Sulfonyl-1,2,3-triazoles react with water in the presence of a rhodium
catalyst to produce α-amino ketones in high yield. This transformation formally
achieves 1,2-aminohydroxylation of terminal alkynes in a regioselective fashion
in combination with a copper(I)-catalyzed 1,3-dipolar cycloaddition with N-sulfonyl
azides.
T. Miura, T. Biyajima, T. Fujii, M. Murakami, J. Am. Chem. Soc., 2012,
134, 194-196.
A totally regioselective transformation of aromatic N-4-methoxyphenylaziridine
2-carboxamides into 2-aminoamides is promoted by active manganese (Mn*). α-Amino
ketones can be readily obtained by reaction of morpholine-derived 2-aminoamides
with organolithium compounds.
J. M. Concellón, H. Rodríguez-Solla, V. del Amo, P. Díaz, J. Org. Chem., 2010,
75, 2407-2410.
Structurally and functionally diverse N-carbamoylamino acids were
obtained through the alkylation of monosubstituted parabanic acids followed by
hydrolysis of the intermediate products in very good yields and excellent purity.
A. V. Bogolubsky, S. V. Ryabukhin, G. G. Pakhomov, E. N. Ostapchuk, A. N.
Shivanyuk, A. A. Tolmachev, Synlett, 2008,
2279-2282.
