REGIOSELECTIVE ELECTROPHILIC REACTIONS ON SUBSTITUTED PURINES - PREDOMINANT INTERMEDIACY OF 6-PURINYL OR 8-PURINYL CARBANIONS

被引:46
作者
LEONARD, NJ
BRYANT, JD
机构
[1] Roger Adams Laboratory, School of Chemical Sciences, University of Illinois, Urbana
关键词
D O I
10.1021/jo00393a033
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
6-Iodo-9-(tetrahydropyran-2-yl)purine (1) was found to undergo reaction with n-butyllithium in THF to produce, depending upon the time and temperature of the reaction, either 6-lithio- or 8-lithio-9-(tetrahydropyran-2-yl)purine in predominance. Shorter reaction time and lower temperature were necessary for the utilization of the 6-lithio derivative, while longer reaction time and higher operating temperature favored the equilibration to the 8-lithio isomer. These carbanions were treated with a variety of electrophiles to produce the corresponding 6- or 8-substituted compounds (3 or 4). 6-Chloro-9-(tetrahydropyran-2-yl)purine (7) was treated similarly with nbutyllithium in THF at -78°C and was then caused to react with various electrophiles to give 8-substituted 6-chloro-9-(tetrahydropyran-2-yl)purines (8). The chloro substituent in 8 was removed by hydrogenolysis or displaced with NH3 to give the correspondingly substituted purines (4) or adenines (9). © 1979, American Chemical Society. All rights reserved.
引用
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页码:4612 / 4616
页数:5
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