American Chemical Society
jo5025249_si_001.pdf (523.47 kB)

Metal-Free, One-Pot, Sequential Protocol for Transforming α,β-Epoxy Ketones to β‑Hydroxy Ketones and α‑Methylene Ketones

Download (523.47 kB)
journal contribution
posted on 2015-02-06, 00:00 authored by Eietsu Hasegawa, Saki Arai, Eiji Tayama, Hajime Iwamoto
A new sequential, one-pot protocol for transforming 1,3-disubstituted 2,3-epoxy ketones to β-hydroxy ketones and α-methylene ketones has been developed. Reaction of epoxy ketones with boron trifluoride etherate (BF3·OEt2) generates the cationic intermediates by regioselective epoxide ring opening and an acyl shift. Then, a treatment of these cations with 2-aryl-1,3-dimethylbenzimidazolines (DMBIH) results in formation of 1,2-disubstituted 3-hydroxy ketones. DMBIH serves as a hydride donor in the second step of this process. Finally, the β-hydroxy ketones can be converted to 1,2-disubstituted 2-methylene ketones by treatment with methanesulfonic acid or a combination of methanesulfonyl chloride and triethylamine. Importantly, the sequential steps involved in formation of the α-methylene ketone products can be carried out in one pot.