Reaction of N-acyl-α-triphenylphosphonio-α-amino acid esters with organic bases:: Mechanism of the base-catalyzed nucleophilic substitution of the triphenylphosphonium group

被引：8

作者：

Mazurkiewicz, R ^{[1
]}

Grymel, M ^{[1
]}

机构：

[1] Silesian Tech Univ, Inst Organ Chem & Technol, PL-44100 Gliwice, Poland

来源：

MONATSHEFTE FUR CHEMIE | 2002年 / 133卷 / 09期

关键词：

N-alpha-triphenylpliosphonioglycinates; nucleophilic substitution; synthetic equivalents of alpha-amino acid alpha-cations; glycine functionalization;

D O I：

10.1007/s007060200090

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Reactions of N-acyl-alpha-triphenylphosphonio-alpha-amino acid methyl esters with organic bases (triethylamine or DBU) were investigated as the crucial step of the base-catalyzed displacement of the triphenylphosphonium group by nucleophiles. It was proved that N-acyl-alpha-triphenylphosphonioglycinates are transformed to an equilibrium mixture of the corresponding N-acyliminoacetates and N-acyl-alpha-triphenylphosphoranylidene glycinates by bases. In the case of N-acyl-alpha-triphenylphosphonio-alpha-amino acid esters with quaternary alpha-carbon, the alpha-substituted homologues of the N-acyliminoacetates were detected to be the only primary reaction product which, however, can undergo further tautomerization to the Corresponding alpha,beta-dehydro-alpha-amino acid derivatives. In both these cases the reaction of N-acyl-alpha-triphenylphosphonio-alpha-amino acid esters with nucleophiles proceeds via the addition of a nucleophile to the activated C=N double bond of the N-acylimino intermediate.

引用

页码：1197 / 1204

页数：8

共 11 条

[1] NEW SYNTHESIS OF N-ACYL AROMATIC ALPHA-AMINO-ACIDS - AMIDOALKYLATION OF AROMATIC AND HETEROCYCLIC-COMPOUNDS WITH GLYOXYLIC-ACID DERIVATIVES [J].

BENISHAI, D ;

SATATY, I ;

BERNSTEIN, Z .

TETRAHEDRON, 1976, 32 (13) :1571-1573

[2] SYNTHESIS OF N-SUBSTITUTED AZIRIDINE-2-CARBOXYLATES [J].

BERNSTEIN, Z ;

BENISHAI, D .

TETRAHEDRON, 1977, 33 (08) :881-883

[3] NEW SYNTHESES OF ALPHA-AMINO-ACIDS BASED ON N-ACYLIMINO ACETATES [J].

BRETSCHNEIDER, T ;

MILTZ, W ;

MUNSTER, P ;

STEGLICH, W .

TETRAHEDRON, 1988, 44 (17) :5403-5414

[4] REACTION OF ACYLAMINOBROMOMALONATES AND ACYLAMINOBROMOACETATES WITH TRIALKYLPHOSPHITES - A SIMPLE SYNTHESIS OF ETHYL 2-AMINO-2-(DIETHOXYPHOSPHORYL)ACETATE [J].

KOBER, R ;

STEGLICH, W .

LIEBIGS ANNALEN DER CHEMIE, 1983, (04) :599-609

[5] SYNTHESIS OF DIASTEREO- AND ENANTIOMERICALLY PURE ALPHA-AMINO-GAMMA-OXO ACID ESTERS BY REACTION OF ACYLIMINOACETATES WITH ENAMINES DERIVED FROM 6-MEMBERED KETONES [J].

KOBER, R ;

PAPADOPOULOS, K ;

MILTZ, W ;

ENDERS, D ;

STEGLICH, W ;

REUTER, H ;

PUFF, H .

TETRAHEDRON, 1985, 41 (09) :1693-1701

[6] N-Acyl-a-triphenylphosphonioglycinates:A Novel Cationic Glycine Equivalent and its Reactions with Heteroatom NucleophilesN-Acyl-α-triphenylphosphonionoglycinate: Ein neues kationisches Glycinäquivalent und seineReaktionen mit Heteroatomnucleophilen [J].

Roman Mazurkiewicz ;

Mirosława Grymel .

Monatshefte für Chemie / Chemical Monthly, 1999, 130 (4) :597-604

[7] A new synthesis of α-amino acid derivatives by reaction of N-acyl-α-triphenylphosphonioglycinates with carbon nucleophiles [J].

Mazurkiewicz, R ;

Grymel, M .

PHOSPHORUS SULFUR AND SILICON AND THE RELATED ELEMENTS, 2000, 164 :33-43

[8]

MAZURKIEWICZ R, 1998, 18 EUR C HET CHEM RO, pB34

[9]

MAZURKIEWICZ R, 1998, 18 EUR C HET CHEM RO, pB33

[10]

MUNSTER P, 1987, SYNTHESIS-STUTTGART, P223

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