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Productive Asymmetric Synthesis of All Four Diastereomers of 3‐( trans ‐2‐Nitrocyclopropyl)alanine from Glycine with ( S )‐ or ( R )‐2‐[( N‐ Benzylprolyl)amino]benzophenone as a Reusable Chiral Auxiliary
Author(s) -
Larionov Oleg V.,
Savel'eva Tatyana F.,
Kochetkov Konstantin A.,
Ikonnokov Nikolai S.,
Kozhushkov Sergei I.,
Yufit Dmitrii S.,
Howard Judith A. K.,
Khrustalev Viktor N.,
Belokon Yuri N.,
de Meijere Armin
Publication year - 2003
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200390131
Subject(s) - diastereomer , chemistry , alkylation , moiety , alanine , schiff base , amino acid , crystallization , stereochemistry , medicinal chemistry , organic chemistry , catalysis , biochemistry
All four diastereomers of 3‐( trans ‐2‐nitrocyclopropyl)alanine ( 3 ) were prepared by asymmetrically induced α‐C alkylation of the glycine moiety in the [( S )‐ or ( R )‐Schiff base]Ni II complex 7 , employing racemic trans ‐1‐(iodomethyl)‐2‐nitrocyclopropane ( 8 ) as the alkylating agent. A notable difference in solubility between the two diastereomeric products 9a / 9b [when ( S )‐ 7 was used as starting material] or 9d / 9e [when ( R )‐ 7 was employed] allowed for their separation from the same reaction mixture. All the diastereomers of 3‐( trans ‐2‐nitrocyclopropyl)alanine ( 3 ) were produced upon brief exposure of the alkylation products 9 to dilute hydrochloric acid, with subsequent purification by ion‐exchange chromatography and crystallization. The absolute configurations of the nickel complexes 9a − e were established by X‐ray crystallographic analyses. In addition, the X‐ray crystal structure of (2 S ,1′ S ,2′ R )‐ 3 was determined to confirm the convergence of the configurations of the parent nickel complexes 9 with those of the amino acids 3 derived from them. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)