Synthesis of bridged azabicyclic structures via ring-closing olefin metathesis

被引:105
作者
Neipp, CE [1 ]
Martin, SF [1 ]
机构
[1] Univ Texas, Dept Chem & Biochem, Austin, TX 78712 USA
关键词
D O I
10.1021/jo0349936
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
A new strategy for the facile synthesis of azabicyclo[m.n.1]alkenes (m = 3-5; n = 3, 2) has been developed that involves the ring-closing metathesis (RCM) reaction of cis-2,6-dialkenyl-N-acyl piperidine derivatives. The requisite 2,6-dialkenylpiperidines may be readily prepared in six steps starting from glutarimide (11) or three steps from 4-methoxypyridine (25). In one example that establishes the practical utility of the procedure, the functionalized 8-azabicyclo [3.2.1] octane 32, which is a potential intermediate for the syntheses of various tropane alkaloids, was prepared. Additionally, a new route for the construction of the bridged tetrahydro-beta-carboline ring system 5 has been developed that features the ring-closing metathesis of the enyne 45 to construct the bridging ring in 46. This concise route to 46 also features a potentially general and useful procedure for the one-step preparation of a terminal alkyne from an ester function. Selective oxidation of the vinyl group in 46 afforded the unsaturated aldehyde 47, which may serve as a useful intermediate in syntheses of several Sarpagine alkaloids.
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收藏
页码:8867 / 8878
页数:12
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