Ruthenium-catalyzed cycloaddition of 1,6-diynes and nitriles under mild conditions: Role of the coordinating group of nitriles
Ruthenium-catalyzed cycloaddition of 1,6-diynes and nitriles under mild conditions: Role of the coordinating group of nitriles
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DOI：
10.1002/chem.200600176
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发表时间：
2006-07-17
影响因子：
4.3
通讯作者：
Itoh, Kenji
中科院分区：
文献类型：
--
作者：
Yamamoto, Yoshihiko;Kinpara, Keisuke;Itoh, Kenji
在催化量的 [Cp*RuCl(cod)]（Cp*=五甲基环戊二烯基，cod=1,5-环辛二烯）存在下，1,6-二炔在环境温度下与带有配位基团的亚硝酸盐（例如二氰化物或 α-卤腈）进行化学和区域选择性反应，得到双环吡啶。对腈组分的仔细筛选表明，CC三键或杂原子取代基（例如甲氧基和甲硫基）被证明可以充当配位基团，而C=C或C=0双键和氨基则无法促进环加成。这表明具有多个it键或孤对的配位基团对于腈组分是必需的。
In the presence of a catalytic amount of [Cp*RuCl(cod)] (Cp* = pentamethylcyclopentadienyl, cod=1,5-cyclooctadiene), 1,6-diynes were allowed to react chemo- and regioselectively with nitrites bearing a coordinating group, such as dicyanides or alpha-halonitriles, at ambient temperature to afford bicyclic pyridines. Careful screening of nitrile components revealed that a C C triple bond or heteroatom substituents, such as methoxy and methylthio groups, proved to act as the coordinating groups, whereas C=C or C=0 double bonds and amino groups failed to promote cycloaddition. This suggests that coordinating groups with multiple it-bonds or lone pairs are essential for the nitrile components.