Asymmetric Synthesis of 4,4-(Difluoro)glutamic Acid Via Chiral Ni(II)-Complexes of Dehydroalanine Schiff Bases. Effect of the Chiral Ligands Structure on the Stereochemical Outcome

Overview

Journal ChemistryOpen

Specialty Chemistry

Date 2020 Feb 5

PMID 32015956

Citations 2

Authors

Yoshinori Tokairin

Yuhei Shigeno

Jianlin Han

Gerd-Volker Roschenthaler

Hiroyuki Konno

Hiroki Moriwaki

Vadim A Soloshonok

Affiliations

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Abstract

Four differently substituted chiral Ni(II)-complexes of dehydroalanine Schiff base were prepared and reacted with BrCFCOOEt/Cu under the standard reaction conditions. The observed diastereoselectivity was found to depend on the degree and pattern of chlorine substitution for hydrogen in the structure of the dehydroalanine complexes. The unsubstituted complex gave the ratio of diastereomers ()(2)/()(2) of 66/34. On the other hand, introduction of chlorine atoms in the strategic positions on the chiral ligands allowed to achieve a practically attractive diastereoselectivity of (∼98.5/1.5). Diastereomerically pure major product was disassembled to prepare 9-fluorenylmethyloxycarbonyl (Fmoc) derivative of ()-4,4-difluoroglutamic acid.

Citing Articles

Asymmetric Synthesis of Tailor-Made Amino Acids Using Chiral Ni(II) Complexes of Schiff Bases. An Update of the Recent Literature.

Zou Y, Han J, Saghyan A, Mkrtchyan A, Konno H, Moriwaki H Molecules. 2020; 25(12).

PMID: 32545684 PMC: 7356839. DOI: 10.3390/molecules25122739.

Asymmetric Synthesis of 4,4-(Difluoro)glutamic Acid via Chiral Ni(II)-Complexes of Dehydroalanine Schiff Bases. Effect of the Chiral Ligands Structure on the Stereochemical Outcome.

Tokairin Y, Shigeno Y, Han J, Roschenthaler G, Konno H, Moriwaki H ChemistryOpen. 2020; 9(1):93-96.

PMID: 32015956 PMC: 6988766. DOI: 10.1002/open.201900343.

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