Selective syntheses of metalated pyridines from two different unsymmetrical acetylenes, a nitrile, and a titanium(II) alkoxide.
Selective syntheses of metalated pyridines from two different unsymmetrical acetylenes, a nitrile, and a titanium(II) alkoxide.
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DOI：
10.1002/chin.200233154
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发表时间：
2002-03
影响因子：
15
通讯作者：
D. Suzuki;R. Tanaka;H. Urabe;F. Sato
中科院分区：
文献类型：
--
作者：
D. Suzuki;R. Tanaka;H. Urabe;F. Sato
两种不同的，不对称的乙炔和对甲苯磺酰腈与二价钛醇盐试剂，Ti（O-i-Pr）4/2 i-PrMgCl的环三聚反应，以高度选择性的方式产生单一的吡啶基钛化合物。这些金属化的吡啶通过氘解得到相应的氘代吡啶，并进行碘解和铜催化的烷基化，以证明其合成的实用性。或者，由相同的钛（II）醇盐介导的烷氧基化物、末端乙炔和α-烷氧基腈的不同类型的环三聚反应再次以高度选择性的方式进行，得到具有钛酸化侧链的单一吡啶。
Cyclotrimerization of two different, unsymmetrical acetylenes and p-toluenesulfonylnitrile with a divalent titanium alkoxide reagent, Ti(O-i-Pr)4/2 i-PrMgCl, yielded single pyridyltitanium compounds in a highly selective manner. These metalated pyridines were confirmed by deuteriolysis to give the corresponding deuterated pyridines and underwent iodinolysis and copper-catalyzed alkylation to demonstrate their synthetic utility. Alternatively, a different type of cyclotrimerization of an alkynamide, terminal acetylenes, and alpha-alkoxynitriles mediated by the same titanium(II) alkoxide again proceeded in a highly selective manner to give single pyridines having a titanated side chain.