Synthesis of 3‐Acyl‐4‐alkenylpyrrolidines by Platinum‐Catalyzed Hydrative Cyclization of Allenynes
Synthesis of 3‐Acyl‐4‐alkenylpyrrolidines by Platinum‐Catalyzed Hydrative Cyclization of Allenynes
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DOI：
10.1002/hlca.200690165
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发表时间：
2006-08
影响因子：
1.8
通讯作者：
T. Matsuda;S. Kadowaki;M. Murakami
中科院分区：
文献类型：
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作者：
T. Matsuda;S. Kadowaki;M. Murakami
当在 70° 下用催化量的 PtCl2 的 MeOH 溶液处理时，一系列氮系联烯炔 (‘5-aza-1,2-dien-7-ynes’) 1 转化为相应的 3-酰基-4-烯基吡咯烷 3。初始 Pt 促进的环化形成非经典碳阳离子中间体。与甲苯中的环异构化产生双环环丁烯2相反，中间体通过添加氧亲核试剂被拦截以实现正式的水合环化。
A series of nitrogen-tethered allenynes (‘5-aza-1,2-dien-7-ynes’) 1 were transformed to the corresponding 3-acyl-4-alkenylpyrrolidines 3 when treated with a catalytic amount of PtCl2 in MeOH at 70°. Initial Pt-promoted cyclization forms a nonclassical carbocationic intermediate. In contrast to the cycloisomerization in toluene, which produced the bicyclic cyclobutenes 2, the intermediate is intercepted by addition of an oxygen nucleophile to achieve the formal hydrative cyclization.