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

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1991年 / 56卷 / 07期

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.

引用

页码：2386 / 2390

页数：5

共 24 条

[11] SYNTHESIS AND CHEMISTRY OF 5,6-DIHYDROPYRIDINIUM SALT ADDUCTS - SYNTHONS FOR GENERAL ELECTROPHILIC AND NUCLEOPHILIC-SUBSTITUTION OF THE PIPERIDINE RING-SYSTEM [J].

GRIERSON, DS ;

HARRIS, M ;

HUSSON, HP .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1980, 102 (03) :1064-1082

[12] A 3-STEP SYNTHESIS OF DELTA-AMINOLEVULINIC-ACID [J].

HERDEIS, C ;

DIMMERLING, A .

ARCHIV DER PHARMAZIE, 1984, 317 (04) :304-306

[13]

HOULIHAN WJ, 1981, BURGERS MED CHEM 3, P1095

[14] DIE ACYLIERUNG DER N.N-DIMETHYL-ARYLAMIN-OXYDE - DER MECHANISMUS DER POLONOVSKI-REAKTION [J].

HUISGEN, R ;

BAYERLEIN, F ;

HEYDKAMP, W .

CHEMISCHE BERICHTE-RECUEIL, 1959, 92 (12) :3223-3241

[15]

JOHNSON MR, 1981, BURGERS MED CHEM 3, P732

[16]

JOKELA R, 1985, HETEROCYCLES, V23, P1707

[17]

JULIA M, 1968, B SOC CHIM FR, P987

[18]

KALINOWSKI HO, 1988, CARBON 13 NMR SPECTR, P499

[19] BRIDGED-RING NITROGEN-COMPOUNDS .1. SYNTHESIS OF A 2,3,4,5-TETRAHYDRO-1,4-ETHANO-1-BENZAZEPIN-5(1H)-ONE [J].

LENNON, M ;

PROCTOR, GR .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1979, (08) :2009-2012

[20] UNSATURATED AMINES .10. THE MERCURIC ACETATE ROUTE TO SUBSTITUTED PIPERIDINES, DELTA-2-TETRAHYDROPYRIDINES AND DELTA-2-TETRAHYDROANABASINES [J].

LEONARD, NJ ;

HAUCK, FP .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1957, 79 (19) :5279-5292

← 1 2 3 →