Categories: C-C Bond Formation > Nitrogen-containing molecules >
Synthesis of α-Amino Acids and Derivatives
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Recent Literature

Diethyl N-Boc-iminomalonate, prepared on multi-gram scale, served as
a stable and highly reactive electrophilic glycine equivalent which reacted
with organomagnesium compounds affording substituted aryl N-Boc-aminomalonates.
Subsequent hydrolysis produced arylglycines.
P. Cali, M. Begtrup, Synthesis,
2002, 63-64.

A new method for the Rh(I)-catalyzed addition of arylboronic acids to chiral
N-tert-butanesulfinyl imino esters allows the asymmetric
synthesis of arylglycine derivatives in high yields and
diastereoselectivities for various functionalized arylboronic acids.
M. A. Beenen, D. J. Weix, J. A. Ellman, J. Am. Chem. Soc.,
2006,
128, 6304-6305.

An efficient method for the asymmetric synthesis of anti-β-hydroxy-α-amino
acid derivatives is based on highly enantio- and diastereoselective aldol
reactions of the silicon enolate derived from N-trifluoroacetylglycinate
with aldehydes using a chiral zirconium catalyst.
J. Kobayashi, M. Nakamura, Y. Mori, Y. Yamashita, S. Kobayashi, J. Am.
Chem. Soc.,
2004,
126, 9192-9193.

A highly efficient direct asymmetric aldol reaction of a glycinate Schiff
base with aldehydes has been achieved under mild biphasic conditions with
excellent stereochemical control, using a chiral quaternary ammonium salt as
a phase-transfer catalyst.
T. Ooi, M. Kameda, M. Taniguchi, K. Maruoka, J. Am. Chem. Soc.,
2004,
126, 9685-9694.

The regioselective opening of Bn2N-α-methylserine-β-lactone
with organocuprates gave enantiopure α-methyl amino acids in excellent yields.
N. D. Smith, A. M. Wohlrab, M. Goodman, Org. Lett., 2005,
7, 255-258.

In the presence of a catalytic amount of Cu(OTf)2 and a chiral
diamine ligand, various N-acylimino esters reacted smoothly with
silyl enol ethers and alkyl vinyl ethers to afford the corresponding
Mannich-type adducts in high yields with high diastereo- and
enantioselectivities. The reaction mechanism is discussed.
S. Kobayashi, R. Matsubara, Y. Nakamura, H. Kitagawa, M. Sugiura, J. Am.
Chem. Soc., 2003,
125, 2507-2515.

Direct catalytic, enantioselective, anti-selective Mannich-type
reactions between unmodified ketones and α-imino esters using 5-10 mol % of
(R)-3-pyrrolidinecarboxylic or (R)-β-proline as catalyst in
2-PrOH at room temperature gave products in good yields with high diastereo-
and enantioselectivities.
H. Zhang, M. Mifsud, F. Tanaka, C. F. Barbas, III, J. Am. Chem. Soc.,
2006,
128, 9630-9631.

Proline-catalyzed Mannich-type reactions of
N-PMP-protected α-imino ethyl glyoxylate with a variety of unmodified
ketones provided functionalized α-amino acids in high yields with excellent
regio-, diastereo-, and enantioselectivities. In reactions involving ketone
donors where diastereoisomeric products could be formed, two adjacent
stereogenic centers were created simultaneously upon carbon-carbon bond
formation with complete syn-stereocontrol.
A. Cordova, W. Notz, G. Zhong, J. M. Betancort, C. F. Barbas, J. Am.
Chem. Soc., 2002,
124, 1842-1843.

Proline-catalyzed Mannich-type reactions of
N-PMP-protected α-imino ethyl glyoxylate with a variety of unmodified
aliphatic aldehydes provided functionalized α-amino acids in high yields
with excellent enantioselectivities. The diastereoselectivity of the
reaction increased with the bulkiness of the substituents of the aldehyde
donor.
A. Cordova, W. Notz, G. Zhong, J. M. Betancort, C. F. Barbas, J. Am.
Chem. Soc., 2002,
124, 1866-1867.

A direct highly anti-selective and enantioselective asymmetric
Mannich reaction using a novel axially chiral amino
trifluoromethanesulfonamide has been developed. Reactions between aldehydes
and
N-PMP-protected α-imino ethyl glyoxylate proceed smoothly to give β-amino
aldehydes with high anti/syn ratio and enantioselectivity.
T. Kano, Y. Yamaguchi, O. Tokuda, K. Maruoka, J. Am. Chem. Soc.,
2005,
127, 16408-16409.

(3R,5R)-5-methyl-3-pyrrolidinecarboxylic acid as catalyst for
Mannich-type reactions afforded anti-products in good yields with
excellent diastereo- and enantioselectivities under mild conditions and low
catalyst loadings.
S. Mitsumori, H. Zhang, P. H.-Y. Cheong, K. N. Houk, F. Tanaka, C. F.
Barbas, III, J. Am. Chem. Soc.,
2006,
128, 1040-1041.

Chelated amino acid ester enolates are excellent nucleophiles for allylic
alkylations. With these enolates, even terminal π-allyl palladium complexes react
without significant isomerization.
K. Krämer, U. Kazmaier, J. Org. Chem., 2006,
71, 8950-8953.

A Lewis acid-catalyzed three-component, mild, highly atom econocial,
direct-type Mannich reaction of simple aromatic and enolizable aliphatic
aldehydes, secondary amines, and glycine derivatives affords various
synthetically important
anti-α,β-diamino ester derivatives in high yields with high
diastereoselectivities.
M. M. Salter, J. Kobayashi, Y. Shimizu, S. Kobayashi, Org. Lett.,
2006,
8, 3533-3536.

Chiral complexes of calcium promote asymmetric 1,4-addition reactions and [3+2]
cycloaddition reactions of α-amino acid derivatives with α,β-unsaturated
carbonyl compounds. The reactions proceeded smoothly in the presence of 5-10 mol
% of the chiral calcium catalyst to afford the desired adducts in high yields
with high diastereo- and enantioselectivities.
S. Saito, T. Tsubogo, S. Kobayashi, J. Am. Chem. Soc., 2007,
129, 5364-5365.

Homoallylic α-amino esters and amines were prepared via a Pd(II)-catalyzed
coupling of 1,2-nonadiene and boronic acids with ethyl iminoacetate or aliphatic,
aromatic, and heteroaromatic imines.
C. D. Hopkins, H. C. Malinakova, Org. Lett., 2006,
8, 5971-5974.
