Highly efficient methyl ketone synthesis with photoactivated acetone and olefins assisted by Mg(II)-exchanged zeolite Y.
We previously found that photoirradiation of an acetone/water mixture containing olefins affords the corresponding methyl ketones highly efficiently and selectively via a water-assisted C-C coupling between the acetonyl radical and olefins (Org. Lett. 2008, 10, 3117-3120). The reaction proceeds at room temperature without any additives and has a potential to be a powerful method for methyl ketone synthesis. Here we report that an addition of Mg(2+)-exchanged zeolite Y (MgY) to the above photoreaction system accelerates the methyl ketone formation, while maintaining high selectivity. Ab initio molecular orbital calculation reveals that the accelerated methyl ketone formation is due to the electrostatic interaction between Mg(2+) and excited-state acetone. This leads to a charge polarization of the carbonyl moiety of excited-state acetone and accelerates the hydrogen abstraction from ground-state acetone (acetonyl radical formation). This promotes efficient addition of the acetonyl radical to olefins, resulting in methyl ketone formation enhancement. Adsorption experiments reveal that accumulation of olefins inside the zeolite pore also affects efficient radical addition to olefins. The present process successfully produces various methyl ketones with very high yield, and the MgY recovered can be reused for further reaction without loss of activity.
Tsukamoto
Daijiro
D
Research Center for Solar Energy Chemistry and Division of Chemical Engineering, Graduate School of Engineering Science, Osaka University, Toyonaka 560-8531, Japan.
Shiraishi
Yasuhiro
Y
Hirai
Takayuki
T
D000096:Acetone / Q000737:chemistry*; D000475:Alkenes / Q000737:chemistry*; D002384:Catalysis; D018360:Crystallography, X-Ray; D007659:Ketones / Q000138:chemical synthesis*; D008274:Magnesium / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008956:Models, Chemical; D010777:Photochemistry; D013237:Stereoisomerism; D017641:Zeolites / Q000737:chemistry*
D000475:Alkenes; D007659:Ketones; D017641:Zeolites; D000096:Acetone; D008274:Magnesium