A TRANSANNULAR ROUTE FOR STEREOSPECIFIC SYNTHESIS (+/-)-ISORETRONECANOL

被引:59
作者
LEONARD, NJ
SATO, T
机构
[1] Department of Chemistry and Chemical Engineering, University of Illinois, Urbana
关键词
D O I
10.1021/jo01256a064
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
A transannular reaction has been utilized effectively for the stereospecific synthesis of the pyrrolizidine alkaloid derivative (±)-isoretronecanol. The keto ester, ethyl 1-benzyl-1-azacyclooctan-5-one-4-carboxylate, resulting from the high-dilution Dieckmann cyclization of diethyl γ,γ′-benzyliminobisbutyrate, was converted into its transannular salt, ethyl 4-benzyl-8-hydroxypyrrolizidine-1-carboxylate perchlorate. Hydrogenation of this compound using palladium-on-charcoal catalyst produced ethyl (±)-isoretronecanolate perchlorate, from which the base was liberated and reduced to (± )-isoretronecanol with lithium aluminum hydride. 1-Benzyl-1-azaeyclooctan-5-one perchlorate could be hydrogenolyzed to pyrrolizidine perchlorate, 1-benzyl-lazacyclooctan-5-one to pyrrolizidine, ethyl 1-benzyl-1-azacyclooctan-S-one-4-carboxylate to a mixture of ethyl (±)-isoretronecanolate and the corresponding Δ1,8-dehydro ester, and 1-benzyl-1-azacyclodecan-6-one to quinolizidine. The use of the transannular salt as an intermediate in the catalytic hydrogenation step is more efficient than the use of the corresponding base. © 1969, American Chemical Society. All rights reserved.
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页码:1066 / &
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