NDLI: Interplay of ortho- with spiro-cyclisation during iminyl radical closures onto arenes and heteroarenes

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Interplay of ortho- with spiro-cyclisation during iminyl radical closures onto arenes and heteroarenes

Content Provider	Directory of Open Access Journals (DOAJ)
Author	John C. Walton Roy T. McBurney
Abstract	Sensitised photolyses of ethoxycarbonyl oximes of aromatic and heteroaromatic ketones yielded iminyl radicals, which were characterised by EPR spectroscopy. Iminyls with suitably placed arene or heteroarene acceptors underwent cyclisations yielding phenanthridine-type products from ortho-additions. For benzofuran and benzothiophene acceptors, spiro-cyclisation predominated at low temperatures, but thermodynamic control ensured ortho-products, benzofuro- or benzothieno-isoquinolines, formed at higher temperatures. Estimates by steady-state kinetic EPR established that iminyl radical cyclisations onto aromatics took place about an order of magnitude more slowly than prototypical C-centred radicals. The cyclisation energetics were investigated by DFT computations, which gave insights into factors influencing the two cyclisation modes.
Related Links	https://doi.org/10.3762/bjoc.9.120
e-ISSN	18605397
DOI	10.3762/bjoc.9.120
Journal	Beilstein Journal of Organic Chemistry
Issue Number	1
Volume Number	9
Language	English
Publisher	Beilstein-Institut
Publisher Date	2013-01-01
Publisher Place	Germany
Access Restriction	Open
Subject Keyword	Science Organic Chemistry Cyclisation Epr Spectroscopy Free Radicals Heterocycles Oxime Carbonates
Content Type	Text
Resource Type	Article

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