D. Ben-Ishai

Amidoalkylation of mercaptans with glyoxylic acid derivatives

Abstract The synthesis of α-alkyl mercaptohippuric acid (3a–d), N-benzyloxycarbonyl-α-methylthioglycine (3e) and their methyl esters (5a–d) by the amido-alkylation of mercaptans with α-hydroxyhippuric acid (2a), α-hydroxy-N-benzyloxycarbonylglycine (2b) and their methoxymethyl ester derivatives 4a and 4b is described. Oxidation with m-chloroperbenzoic acid afforded the corresponding sulfoxides and sulfones and treatment with N-bromosuccinimide in methanol or chlorine in carbon tetrachloride solution exchanged the sulfur containing side chain for a methoxy or a chloro group respectively. (4a, 8).

Synthesis of N-substituted aziridine-2-carboxylates

Abstract The synthesis of the methyl esters of N -methoxycarbonyl- and N -benzyloxycarbonylaziridine-2-carboxylic acid 2 by reacting methyl 2-chloro- N -carbalkoxyglycinate 1 with diazomethane is described. The aziridines were readily converted to derivatives of O -methylserine 5 and S -methylcysteine 6 .

A new synthesis of n-acyl aromatic α-amino acids—amidoalkylation of aromatic and heterocyclic compounds with glyoxylic acid derivatives

Abstract The synthesis of N-acyl derivatives of aromatic α-amino acids 5 by the amidoalkylations of aromatic and heterocyclic compounds with glyoxylic acid amide adducts is described.

A new synthesis of amino acids—II: Amidoalkylation of olefins with glyoxylic acid derivatives

Abstract A new synthesis of leucine, aspartie acid, aspartic acid semialdehyde and unsaturated N -acyl-α amino acid from olefins and glyoxylic acid-primary amide adducts is described. The chemistry and stereochemistry of the intermediate oxazines 7 and α-amidobutyrolactones 8 is also discussed

A new synthesis of α-amino acids—III: Amidoalkylation of active methylene compounds with glyoxylic acid derivatives

Abstract The synthesis of N-acyl derivatives of γ - keto - α - amino acids ( 3, 4, 5 ) by the amidoalkylation of 1,3-dicarbonyl compounds with glyoxylic acid-amide adducts ( 1, 2 ) is described. The γ - keto - α - amino acid derivatives ( 4, 5 ) were further converted to the corresponding butenolides ( 6, 7 ) and to pyrazolylglycine ( 12 ).

N-Benzoylbenzaldimines and N-α-alkoxybenzylbenzamides

Abstract Thermal decomposition of benzylidenebisbenzamide (I) afforded N-benzoylbenzaldimines (II). Some of the chemical and spectroscopic properties of the aldimides and their methanol addition products (IV) are described.

The synthesis of p-substituted d,l-phenylglycines by the amidoalkylation of benzylchloride and N-benzylbenzamide

Abstract The synthesis of p -hydroxymethyl ( 3 ), p -bromomethyl ( 4 ), p -methoxy-methyl ( 5 ), p -methylthiomethyl ( 6 ) and p -aminomethyl-d, 1-phenylglycines by the amidoalkylation of benzylchloride and N-benzylbenzamide with α-hydroxyhippuric acid is described.

The reactions of 5-methoxyhydantoins with conjugated dienes

Abstract 5-Methoxyhydantoins 4, 5 (R = C7H7) and 5 (R = C6H4Cl) were found to react, thermally or in the presence of an acid catalyst with dienes to give the Diels-Alder adducts 9–19. The acid catalyzed reactions were found to be more stereospecific than the thermal reactions and in three cases gave the amidoalkylation products 20, 23, 24.

Amidoalkylation of aromatics with glyoxylic acid-γ-lactam adducts: 2-pyrrolidinone, pyroglutamic acid amide and ester

Abstract A glyoxylic acid-2-pyrrolidinone adduct leads to N-acyliminium-ion induced intermolecular electrophilic aromatic substitution yielding nitrogen-substituted phenylglycine derivatives, whereas the benzylamide of glyoxylic acid-2-pyrrolidinone adduct undergoes intramolecular amidoalkylation to give an isoquinolone type compound. High stereospecifity and enantioselectivity was observed in intermolecular amidoalkylation of benzene using glyoxylic acid-S-pyroglutamic acid ester or amide adducts.

Inter vs intramolecular amidoalkylations of aromatics - a new synthesis of oxindoles, isoquinolones and benzazepinones

Abstract A new synthesis of oxindoles ( 8 ) isoquinolones ( 5 ) and benzazepinones ( 10 ) by the intramolecular amidoalkylation of aromatic amides of bismethoxycarbonylaminoacetic acid ( 4 , 7 , 9 ) is described.