A catalyst-controlled selective synthesis of pyridines and pyrroles

作者：Jiang Yaojia; Park Cheol Min^*

来源：Chemical Science, 2014, 5(6): 2347-2351.

DOI：10.1039/c4sc00125g

We have developed a dual reaction manifold that enables the selective synthesis of both pyridines and pyrroles from the common substrates alpha-diazo oxime ethers. The strong propensity of 1,3-dienyl nitrenes for 4 pi-electrocyclization to give pyrroles could be diverted to 6 pi-electrocyclization via a 1,6-hydride shift or prototropic isomerization, leading to the exclusive formation of pyridines by employing metal nitrene complexes derived from alpha-diazo oxime ethers under Rh(II) catalysis. Furthermore, an orthogonal catalytic system has been identified that promotes the selective formation of 1H-pyrroles from the same substrates by redirecting the reactivity of vinyl 2H-azirine intermediates.

• 出版日期2014