Categories: C-C Bond Formation > Nitrogen-containing molecules >

Synthesis of α-Amino Acids and Derivatives

Related:

Name Reactions

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.