REGIOSELECTIVE OXIDATION OF PIPERIDINE-3 DERIVATIVES - A SYNTHETIC ROUTE TO 2,5-SUBSTITUTED PIPERIDINES

被引:17
作者
COMPERNOLLE, F [1 ]
SALEH, MA [1 ]
VANDENBRANDEN, S [1 ]
TOPPET, S [1 ]
HOORNAERT, G [1 ]
机构
[1] KATHOLIEKE UNIV LEUVEN,ORGAN SYNTH LAB,CELESTIJNENLAAN 200 F,B-3001 LOUVAIN,BELGIUM
关键词
D O I
10.1021/jo00007a025
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Mercuric acetate oxidation of 1-benzyl-3,3-(ethylenedioxy)piperidine (1) and of 3-CO2Et- and 3-CH2OH-substituted piperidines 7-9 was shown to occur regioselectively at the 6-position. Trapping of the resulting 6-iminium ions with cyanide yielded the corresponding 5-substituted 2-piperidinecarbonitriles 5, 10, and 11. However, the 2-iminium ion was formed in the reaction of the N-oxide of 1 with trifluoroacetic anydride; with cyanide this afforded the regioisomeric 3,3-(ethylenedioxy)-2-piperidinecarbonitrile (2). Plausible mechanisms are advanved to explain this contrasting behavior. 1-Benzyl-5,5-(ethylenedioxy)-2-piperidinecarbonitrile (5) was transformed into other piperidine-2,5 derivatives by reaction of the alpha-amino nitrile anion with electrophoresis, followed by reductive decyanation.
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页码:2386 / 2390
页数:5
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