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

Chemical Science
Sripati JanaRene M Koenigs

Abstract

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.

References

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Citations

Dec 12, 2019·Chemistry : a European Journal·Sripati JanaRene M Koenigs
Jan 31, 2020·Chemistry : a European Journal·Amanda F da SilvaIgor D Jurberg
May 20, 2020·Chemistry, an Asian Journal·Yingying XuYong Wu
Oct 17, 2019·Chemistry : a European Journal·Uyen P N TranRene M Koenigs
Aug 6, 2020·Chemistry : a European Journal·Sripati JanaRene M Koenigs
Dec 5, 2020·Chemistry : a European Journal·Alexander Sandvoß, Johannes M Wiest
Apr 19, 2021·The Journal of Organic Chemistry·Shuai ZhaoXin Chen

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