Biomimetic reductive amination of fluoro aldehydes and ketones via [1,3]-proton shift reaction. Scope and limitations

被引:93
作者
Ono, T
Kukhar, VP
Soloshonok, VA
机构
[1] NATL IND RES INST NAGOYA,KITA KU,NAGOYA,AICHI 462,JAPAN
[2] UKRAINIAN ACAD SCI,INST BIOORGAN CHEM & PETROCHEM,UA-253160 KIEV,UKRAINE
关键词
D O I
10.1021/jo960503g
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
A systematic study of azomethine-azomethine isomerizations of the N-benzylimines 2, derived from fluorinated aldehydes or ketones and benzylamine, has been made. The results reveal that, in sharp contrast to hydrocarbon analogs, fluorinated imines of 2 in triethylamine solution undergo isomerizations to give the corresponding N-benzylidene derivatives 5 (for 5/2 K > 32) in good isolated yields. The rates of the isomerizations depend on the starting imine structures and increase in the following order: aryl perfluoroalkyl ketimine 2m, per(poly)fluoroalkyl aldimine 2a,d-g, perfluoroaryl aldimine 2h, alkyl perfluoroalkyl ketimine 2ij. The presence of chlorine or bromine atoms in the alpha-position to the C=N double bond of the starting imine favors a dehydrohalogenation reaction, giving rise to unsaturated products 6-9. The azomethine-azomethine isomerization was studied and proven to proceed essentially (>98%) intramolecularly with isotope exchange experiments. High chemical yields, the simplicity of the experimental procedure, and the low cost of all reagents employed make this biomimetic transamination of fluorocarbonyl compounds a practical method for preparing fluorine-containing amines of biological interest.
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页码:6563 / 6569
页数:7
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