Tandem [4+2]/[3+2] cycloadditions of nitroalkenes .9. Synthesis of (-)-rosmarinecine

被引:75
作者
Denmark, SE
Thorarensen, A
Middleton, DS
机构
[1] Roger Adams Laboratory, Department of Chemistry, University of Illinois, Urbana
关键词
D O I
10.1021/ja961630x
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
(-)-Rosmarinecine (2) is the necine base portion of the pyrrolizidine alkaloid (-)-rosmarinine. (-)-Rosmarinecine is a representative of the group of pyrrolizidines that show a cis relationship between adjacent stereocenters C(1), C(7), and C(7a), in addition to a highly oxygenated skeleton. (-)-Rosmarinecine (2) has been synthesized in eight steps and 14.8% overall yield, as an illustration of a general approach for the construction of pyrrolizidines having this stereochemical feature. The key step in the asymmetric synthesis is a Lewis acid-promoted, tandem inter-[4 + 2]/intra-[3 + 2] cycloaddition between a fumaroyloxy nitroalkene and a chiral vinyl ether.
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收藏
页码:8266 / 8277
页数:12
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