Manganese-catalyzed enantioselective oxidation of C–H bonds of alkanes and silyl ethers to optically active ketones

The (salen)manganese(III) complex-catalyzed oxidation of C–H bonds of symmetrical alkanes and symmetrical 1,3- and 1,4-disilyl ethers with iodosylbenzene gave the corresponding optically active ketones (up to 70% ee) and β- and γ-siloxyketones (up to 93% ee).

Figure optionsDownload as PowerPoint slide

(R)-2-tert-Butyldimethylsiloxy-1-indanoneC15H22O2SiEe = 42%[α]D27=-3.6 (c 0.20, CHCl3)Source of chirality: chiral catalystAbsolute configuration: R

(R)-3-Hydroxy-1-indanoneC9H8O2Ee = 62%[α]D23=-87.5 (c 2.0, CHCl3)Source of chirality: chiral catalystAbsolute configuration: R

(S)-3-tert-Butyldimethylsiloxy-2,2-dimethyl-1-indanoneC17H26O3SiEe = 80%[α]D23=-9.2 (c 0.07, CHCl3)Source of chirality: chiral catalystAbsolute configuration: S