Photochemical ring expansion reactions: synthesis of tetrahydrofuran derivatives and mechanism studies

Chemical Science
Sripati JanaRene M Koenigs


The reaction mechanism of oxygen and sulfur ylide mediated rearrangements is even today a matter of debate. In this report, we describe ring expansion reactions of oxetane and thietane heterocycles that allow probing the underlying reaction mechanism under metal-free, photochemical conditions. This ring expansion proves highly efficient and allows the synthesis of tetrahydrofuran and thiolane heterocycles under mild and operationally simple reaction conditions. These studies reveal marked differences in the stereoselectivity of the ring expansion of oxygen or sulfur ylides, which were further investigated computationally. DFT calculations show that carbenes react under ylide formation and that the corresponding ring expansion reactions proceed via a diradical pathway. The different bond lengths in free oxygen or sulfur ylide intermediates cause the distinctive stereochemical outcome.


May 13, 2010·The Journal of Organic Chemistry·Giovanni GhigoGlauco Tonachini
Aug 20, 2010·The Journal of Organic Chemistry·Ekaterina D ButovaAndrey A Fokin
Oct 30, 2010·Angewandte Chemie·Johannes A BurkhardErick M Carreira
Jun 15, 2011·Chemical Communications : Chem Comm·Deana M JaberMichael P Doyle
Sep 1, 1986·Journal of the American Chemical Society·E J Roskamp, C R Johnson
Mar 14, 2012·Organic Letters·Deana M JaberMichael P Doyle
Sep 16, 2016·Chemical Reviews·James A BullKate F Morgan
Feb 15, 2017·Angewandte Chemie·Tomoya MiuraMasahiro Murakami
Apr 15, 2018·Topics in Current Chemistry·James D NeuhausNuno Maulide
Jun 26, 2018·Chemical Science·Igor D Jurberg, Huw M L Davies
Jul 25, 2018·Chemical Communications : Chem Comm·Tiebo XiaoLei Zhou
Nov 28, 2018·Angewandte Chemie·Renè HommelsheimRene M Koenigs
Dec 14, 2018·Organic & Biomolecular Chemistry·Łukasz W CiszewskiDorota Gryko
Mar 29, 2019·Chemistry : a European Journal·Zhen YangRene M Koenigs
Apr 9, 2019·Chemical Communications : Chem Comm·Feifei He, Rene M Koenigs
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