An electrochemical synthesis of 2-acetoxy-2-amino acid and 3-acetoxy-3-amino acid derivatives

Iwasaki, Tameo; Horikawa, Hiroshi; Matsumoto, Kazuo; Miyoshi, Muneji

doi:10.1021/jo00434a015

Cited by 39 publications

(21 citation statements)

References 4 publications

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“…Hemiesters 1, [25] 2, 3 [26] were synthesized first by alkylation with the appropriate alkyl halide and second by partial saponification. Diacid 4 was prepared by full saponification.…”

Section: Resultsmentioning

confidence: 99%

“…General: 1 The precursors for the substrates diethyl 2-N-acetylamino-2-methylmalonate [25] , diethyl 2-N-acetylamino-2-isopropylmalonate, [32] diethyl 2-N-acetylamino-2-benzylmalonate [33] and ethyl 2-N-acetylamino-2-cyanopropionate [27] and the substrates 2-N-acetylamino-2-ethoxycarbonylpropionic acid (1) [25] and 2-N-acetylamino-2-ethoxycarbonyl-3-phenylpropionic acid (3) [26] were prepared according to the literature. 3,5-Dimethoxybenzoyl chloride was obtained by refluxing the corresponding acid for 2 h in SOCl 2 , followed by bulb-to-bulb distillation in vacuo.…”

Section: Methodsmentioning

confidence: 99%

“…130Ϫ132°C (dec., ȆCO 2 ). IR (KBr): ν ϭ 3360 (NϪH), 1780 cm Ϫ1 (CϭO 2-N-Acetylamino-2-methylmalonic Acid (4): Diethyl 2-N-acetylamino-2-methylmalonate [25] (5.0 g, 21.6 mmol) was added to a solution of KOH (4.90 g, 87.0 mmol) in EtOH (20 mL) and water (10 mL). After stirring for 6 d at room temp., the solvents were removed at room temp.…”

Section: -N-acetylamino-2-ethoxycarbonyl-3-methylbutyric Acid (2)mentioning

confidence: 99%

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α‐Amino Acid Derivatives by Enantioselective Decarboxylation

Brunner

Baur

2003

Eur J Org Chem

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The methodology of enantioselective decarboxylation was applied to 2‐aminomalonic acid derivatives in order to obtain enantio‐enriched amino acid derivatives. Full conversion was achieved stirring racemic N‐acetylated 2‐aminomalonic hemiesters in THF at 70 °C with 10 mol % of a chiral base for 24 h. The catalyst may be recycled. Whereas the commercially available cinchona alkaloids gave poor results, benzamide and benzenesulfonamide derivatives of 9‐amino(9‐deoxy)epicinchonine turned out to be effective catalysts. The best result was obtained with 2‐N‐acetylamino‐2‐ethoxycarbonyl‐3‐phenylpropionic acid as the starting material and N‐(9‐deoxyepicinchonine‐9‐yl)‐4‐methoxybenzamide as the chiral base to give ethyl N‐acetyl‐L‐phenylalaninate in 70% ee. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

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“…Hemiesters 1, [25] 2, 3 [26] were synthesized first by alkylation with the appropriate alkyl halide and second by partial saponification. Diacid 4 was prepared by full saponification.…”

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: -N-acetylamino-2-ethoxycarbonyl-3-methylbutyric Acid (2)mentioning

confidence: 99%

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α‐Amino Acid Derivatives by Enantioselective Decarboxylation

Brunner

Baur

2003

Eur J Org Chem

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“…[13][14][15][16][17][18][19] We have also demonstrated that phosphonium salts 4 are effective and convenient amidoalkylating agents when activated with organic bases (DBU or i-Pr 2 EtN). 15,20,21 The particularly straightforward and useful method for the synthesis of phosphonium salts 4 consists in the electrochemical decarboxylative α-alkoxylation (usually α-methoxylation) of easily accessible N-acyl-α-amino acids (well known as the Hofer-Moest reaction) [22][23][24][25][26][27][28][29][30][31][32][33][34] followed by the displacement of the α-alkoxy group with triphenylphosphonium group by treatment with triphenylphosphine tetrafluoroborate (Scheme 2).…”

Section: Methodsmentioning

confidence: 99%

N-(1-acyloaminoalkyl)amidinium salts derived from DBU or related bases as reactive intermediates in α-amidoalkylation reactions

Październiok-Holewa¹,

Adámek²,

Zielińska³

et al. 2012

Arkivoc

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Abstract1-(N-Acylamino)alkyltriphenylphosphonium salts 4, when treated with DBU, DBN or TBD in CD 3 CN or MeCN, were transformed immediately into the corresponding 1-(Nacylamino)alkylamidinium or guanidinium salts 5. Salts 5 with a proton at the α-position underwent slow transformation to the corresponding enamides 6. 1-(NAcylamino)alkyltriphenylphosphonium salts 4, amidinium or guanidinium salts 5, as well as enamides 6 reacted readily with β-dicarbonyl compounds in the presence of corresponding base under microwave irradiation at 60 o C to give the expected product of α-amidoalkylation of the enolate anion. The role of 1-(N-acylamino)alkylamidinium or guanidinium salts 5 as reactive intermediates in α-amidoalkylation with 1-(N-acylamino)alkyltriphenylphosphonium salts is discussed.

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“…Because of this, the development of enantioselective methods for the preparation of a-amino acids has attracted significant attention from organic chemists. Electrochemical anodic a-alkoxylation is one of the most promising methods for functionalisation of the a position of a-amino acid derivatives and simple peptides [3][4][5][6].…”

Section: Introductionmentioning

confidence: 99%

Investigations on electrochemical α-methoxylation of selected dipeptides

et al. 2011

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Voltamperometric studies on the indirect electrochemical a-methoxylation of Boc-Pro-Gly-OMe and Boc-Val-Gly-OMe in MeOH in the presence of NaCl or NaBr as the mediator suggested that the first reaction step was a direct N-halogenation of the dipeptide by active chlorine or bromine adsorbed on the electrode surface. The kind of mediator (NaCl or NaBr), its concentration, the current density, and the applied electric charge had a significant influence on the reaction course. In the case of Boc-Pro-Gly-OMe, the use of sodium bromide was necessary to obtain a relatively high ratio of a-monomethoxylation to a,a-dimethoxylation. For Boc-Val-Gly-OMe, the selectivity for a-monomethoxylation was close to 100%, independently of the mediator. Optimisation of the selected electrolysis parameters allowed us to significantly improve the yield and selectivity of the a-methoxylation of Boc-Pro-Gly-OMe (Kardassis et al. Tetrahedron 54:3471, 1998) and to obtain good results in the a-methoxylation of Boc-Val-Gly-OMe.

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An electrochemical synthesis of 2-acetoxy-2-amino acid and 3-acetoxy-3-amino acid derivatives

Cited by 39 publications

References 4 publications

α‐Amino Acid Derivatives by Enantioselective Decarboxylation

α‐Amino Acid Derivatives by Enantioselective Decarboxylation

N-(1-acyloaminoalkyl)amidinium salts derived from DBU or related bases as reactive intermediates in α-amidoalkylation reactions

Investigations on electrochemical α-methoxylation of selected dipeptides

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