A catalyst-controlled selective synthesis of pyridines and pyrroles
Date of Issue2014
School of Physical and Mathematical Sciences
UNIST (Ulsan National Institute of Science and Technology)
We have developed a dual reaction manifold that enables the selective synthesis of both pyridines and pyrroles from the common substrates α-diazo oxime ethers. The strong propensity of 1,3-dienyl nitrenes for 4π-electrocyclization to give pyrroles could be diverted to 6π-electrocyclization via a 1,6-hydride shift or prototropic isomerization, leading to the exclusive formation of pyridines by employing metal nitrene complexes derived from α-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.
DRNTU::Science::Chemistry::Organic chemistry::Organic synthesis
© 2014 The Authors. This is the author created version of a work that has been peer reviewed and accepted for publication in Chemical Science, published by Royal Society of Chemistry on behalf of The Authors. It incorporates referee’s comments but changes resulting from the publishing process, such as copyediting, structural formatting, may not be reflected in this document. The published version is available at: [Article DOI: http://dx.doi.org/10.1039/c4sc00125g].