Selective preparation of benzyltitanium compounds by the metalative Reppe reaction. Its application to the first synthesis of alcyopterosin A
Selective preparation of benzyltitanium compounds by the metalative Reppe reaction. Its application to the first synthesis of alcyopterosin A
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DOI：
10.1021/ja027008o
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发表时间：
2002-08-21
影响因子：
15
通讯作者：
Sato, F
中科院分区：
文献类型：
--
作者：
Tanaka, R;Nakano, Y;Sato, F
由两种不同的乙炔和二价钛醇盐试剂Ti（O-i-Pr）_4/2 i-PrMgCl制备的二烷氧基钛环戊二烯与炔丙基溴反应直接得到苄基钛化合物。得到的苄基钛化合物进行氘解，碘解（与I2），或氧化（与O2气体），得到相应的氘标记的化合物，碘化物，或醇，说明其合成的通用性。首次合成alcyopterosin A，二环芳香族倍半萜最近分离和表征，已实现了通过这种方法，开始与乙炔和二炔的适当组合。
Dialkoxytitanacyclopentadienes, prepared from two different acetylenes and a divalent titanium alkoxide reagent, Ti(O-i-Pr)4/2i-PrMgCl, reacted with propargyl bromide to give directly benzyltitanium compounds. The resultant benzyltitanium compounds underwent deuteriolysis, iodinolysis (with I2), or oxygenation (with O2gas) to give the corresponding deuterium-labeled compounds, iodides, or alcohols, illustrating their synthetic versatility. The first synthesis of alcyopterosin A, a bicyclic aromatic sesquiterpenoid recently isolated and characterized, has been achieved by this method, starting with an appropriate combination of an acetylene and a diyne.