Highly regioselective olefination of substituted N,N-dimethylbenzylamines was developed by tuning the acidity of reaction conditions based on analysis of their features. The ortho-functionalized N,N-dimethylbenzylamines were further transformed into 3-(2'-tolyl)propanoic acid and its derivatives under mild conditions. These two transformations could be combined into one pot, and 3-(2'-tolyl)propanoic acid and its derivatives were obtained in moderate to good yields. Mechanistic studies indicated that electrophilic attack on the phenyl ring by the Pd(II) ion assisted by the N,N-dimethylaminomethyl group was a key step during this catalytic transformation, which was controlled by the acidity of the reaction conditions.

Indirect ortho functionalization of substituted toluenes through ortho olefination of N,N-dimethylbenzylamines tuned by the acidity of reaction conditions.

Addition of Et2AlCN and i-PrOH to ketosulfinimines (N-sulfinyl imines) affords corresponding α-alkyl α-amino nitriles in moderate to good yields. The diastereoselectivity is largely dependent on the E/Z isomer ratio of the ketosulfinimine. Hydrolysis of the diastereomerically pure amino nitriles affords enantiopure α-alkyl α-amino acids in moderate to good yields.

Applications of the sulfinimine-mediated asymmetric strecker synthesis to the synthesis of alpha-alkyl alpha-amino acids.

Chiral building blocks for the synthesis of nitrogen‐containing natural products, 5. The enantioselective synthesis of optically active, benzene nucleus‐substituted 1‐phenylethylamines from the corresponding acetophenones

Katalytische asymmetrische Alkylierung von Nucleophilen - asymmetrische Synthese α-alkylierter Aminosäuren†

CD. curves have been recorded for α-aryl-α-amino acids, esters and amides related to α-phenylglycine, α-phenyl-alanine and their N-dimethyl derivatives, and for the corresponding α-cyclohexyl-α-amino acids and esters. Compounds with the (S)-configuration at the single asymmetric carbon atom give strong positive Cotton effects near 220 nm. The conformations of the acids are discussed and compared with those of other α-amino acids.

Optical Rotatory Dispersion and Circular Dichroism Part LXXV: Circular dichroism of some aryl‐amino acids [1]

The stereochemistry of the hydrogenolysis of benzyl-N bonds was studied using S(+)-2-dimethylamino-2-phenyl-propionic acid (I) and its derivatives, and R(−)-2-anilino-2-phenyl-propionic acid (II). The configuration of I was confirmed, that of II established by ORD. measurements, after transformation of the phenyl into cyclohexyl groups. On a palladium catalyst the hydrogenolysis of I, its methyl and ethyl esters and its amide proceeded with 72 to 99% inversion of configuration, that of II with at least 66% inversion. The ester of the quaternary ammonium derivative of I gave as much inversion as retention (= racemisation).

Über die Stereochemie der Hydrogenolyse von N-Benzyl-Bindungen I. Die Hydrogenolyse von Derivaten der 2-Amino-2-phenyl-propionsäure.†

Stereochemie der hydrogenolyse von n-benzyl-bindungen 1. mitt. hydrogenolyse von derivaten der 2-amino-2-phenyl-propionsaeure 2. mitt. deuteriolyse von chiralem n,n-dimethyl-phenylglycin und konfiguration von (+)-phenyl-(2-d)-essigsae

J. A. Garbarino

Papers

Über die Stereochemie der Hydrogenolyse von N-Benzyl-Bindungen I. Die Hydrogenolyse von Derivaten der 2-Amino-2-phenyl-propionsäure.†

Stereochemie der hydrogenolyse von n-benzyl-bindungen 1. mitt. hydrogenolyse von derivaten der 2-amino-2-phenyl-propionsaeure 2. mitt. deuteriolyse von chiralem n,n-dimethyl-phenylglycin und konfiguration von (+)-phenyl-(2-d)-essigsae