Conversion of α,β-unsaturated ketones and α,β-unsaturated esters into α-hydroxy ketones and α-hydroxy esters using Mn(III) catalyst, phenylsilane and dioxygen
AssigneeBoard of Regents, The University of Texas System
InventorsPhilip D. Magnus, Andrew H. Payne
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Abstract
The present invention provides a novel process for the conversion of α,β-unsaturated ketones. This invention is an improvement over existing processes in that it operates at neutral reaction conditions that prevent the formation of side reactions and that it is a single step, which proceeds with complete selectivity and gives a yield that is approximately 30% higher than the currently used processes. An example of this process is the conversion of 16-dehydroprogesterone into 17 α-hydroxyprogesterone.
Claims56
A method for converting α,β-unsaturated ketones to α-hydroxyketones comprising:
- i) obtaining said α,β-unsaturated ketone;
- ii) obtaining a catalyst of the structure:
- where each R is independently hydrogen, a C1-C20 linear, branched or cyclic alkyl, hydroxyalkyl, glycol, polyglycol, amino, nitro, halo, cyano, aryl, heteroaryl, thio, thioalkyl, amide, ester, acyl, carboxy, —NH2, —O(CH2)nCH3 and 0≦n≦20 or —OCH3;
- iii) obtaining a reducing agent;
- iv) combining said ketone, said catalyst and said reducing agent in the presence of dioxygen and a solvent or solvent mixture to form an α-hydroperoxyketone;
- and
- v) reducing said α-hydroperoxyketone to an α-hydroxyketone.
A method for converting 16-dehydroprogesterone to 17 α-hydroxy progesterone comprising:
- i) obtaining said 16-dehydroprogesterone;
- ii) obtaining a catalyst of the structure:
- where each R is independently hydrogen, a C1-C20 linear branched or cyclic alkyl, hydroxyalkyl, glycol, polyglycol, amino, nitro, halo, cyano, aryl, heteroaryl, thio, thioalkyl, amide, ester, acyl, carboxy, —NH2, —O(CH2)nCH3 and 0≦n≦20 or —OCH3;
- iii) obtaining a reducing agent;
- iv) combining said 16-dehydroprogesterone, said catalyst and said reducing agent in the presence of dioxygen and a solvent or solvent mixture to form an α-hydroperoxyketone;
- and
- v) reducing said α-hydroperoxyketone to 17 α-hydroxy progesterone.
A method for reducing β,β-disubstituted ketone or ester comprising:
- i) obtaining said β,β-disubstituted ketone or ester;
- ii) obtaining the catalyst tris(dipivaloylmethanato)manganes(III);
- iii) obtaining a reducing agent;
- iv) combining said ketone or ester, said catalyst and said reducing agent in the presence of dioxygen and a solvent or solvent mixture to produce a hydridic reagent capable of reducing said β,β-disubstituted ketone or ester.
A method for converting α,β-unsaturated esters to α-hydroxyesters comprising:
- i) obtaining said α,β-unsaturated ester;
- ii) obtaining a catalyst of the structure:
- where each R is independently hydrogen, a C1-C20 linear branched or cyclic alkyl, hydroxyalkyl, glycol, polyglycol, amino, nitro, halo, cyano, aryl, heteroaryl, thio, thioalkyl, amide, ester, acyl, carboxy, —NH2, —O(CH2)nCH3 and 0≦n≦20 or —OCH3;
- iii) obtaining a reducing agent;
- iv) combining said ester, said catalyst and said reducing agent in the presence of dioxygen and a solvent or solvent mixture to form an α-hydroperoxyester;
- and
- v) reducing said α-hydroperoxy ester to an α-hydroxyester.
Dependencies are inferred from the claim text.