Enantioselective synthesis of (S)-2-hydroxypropanone derivatives by benzoylformate decarboxylase catalyzed C-C bond formation

Dunnwald, T
Demir, Ayhan Sıtkı
Siegert, P
Pohl, M
Muller, M
Chiral 2-hydroxypropanone derivatives 5a-v, 8a-d, and 10a, b were formed by benzoylformate decarboxylase (BFD) catalyzed C-C bond formation. A donor aldehyde and acetaldehyde as an acceptor were carboligated in aqueous buffer solution with remarkable ease in high chemical yield and good to high optical purity. The substrate range of this thiamin diphosphate dependent enzyme was examined to employ this benzoin condensation type reaction in stereoselective synthesis. The observed dependence of the enantiomeric excess on the substitution pattern could be exploited to design substrates resulting in high selectivity Best substrates with regard to optical purity were meta-substituted benzaldehyde derivatives. To enable a general and convenient applicability of the BFD-catalyzed C-C bond formation, analytical batch experiments were scaled up to give (S)-2-hydroxy ketones in good to high yields on a preparative scale. Further, the solubility of some of the organic substrates in aqueous solution was increased by the use of cyclodextrin or buffer/DMSO mixtures.


Enantioselective synthesis of hydroxy ketones through cleavage and formation of acyloin linkage. Enzymatic kinetic resolution via C-C bond cleavage
Demir, Ayhan Sıtkı; Pohl, M; Janzen, E; Muller, M (2001-01-01)
Both enantiomers of benzoins and (R)-2-hydroxy-1-phenylpropanone analogues were obtained in high yield on a preparative scale starting from aromatic aldehydes, rac-benzoins and aliphatic aldehydes via enzyme-catalysed C-C bond cleavage and C-C bond formation reactions.
Enantioselective decarboxylative michael and aldol reactions with bifunctional squaramide organocatalysts
Bayer, Ezgi; Tanyeli, Cihangir; Department of Chemistry (2018)
The decarboxylative Michael and aldol reactions are quite new in the asymmetric studies and are used for forming new C-C bonds by nucleophilic attack. In the first part of this thesis, decarboxylative Michael reaction of isatylidene malononitriles with ethyl benzoyl acetate was accomplished in the presence of chiral 2- aminoDMAP and quinine derived bifunctional acid/base organocatalysts, which are developed in our research group. In this part, 12 derivatives were synthesized with quinine based 1-adamantyl s...
Enantioselective synthesis of 4,5,6,7-tetrahydro-4-oxo-benzofuran-5-yl acetate and 1-benzyl-4,5,6,7-tetrahydro-4-oxo-1(H)-indol-5-yl acetate using chemoenzymatic methods
Demir, Ayhan Sıtkı; Caliskan, Zerrin; Sahin, Ertan (Elsevier BV, 2007-03-01)
The chemoenzymatic synthesis of both of the enantiomers of pharmacologically interesting compounds such as 4,5,6,7-tetrahydro-4-oxobenzofuran-5-yl acetate (2a), 4,5,6,7-tetrahydro-4-oxo-6,6-dimethylbenzofuran-5-yl acetate (2b), and their hydroxy derivatives 3a, 3b, 1-benzyl4,5,6,7-tetrahydro-4-oxo-1(H)-indol-5-yl acetate (5), starting from 6,7-dihydrobenzofuran-4(5H)-one (la), 6,7-dihydro-6,6-dimethylbenzofuran4(5H)-one (7b), and 1-benzyl-6,7-dihydro-1 H-indol-4(5H)-one (4) are reported. Manganese(III) acet...
Thermal catalytic hydrosilylation of conjugated dienes with triethylsilane in the presence of tricarbonyl(o-xylene)metal (metal = Cr, Mo, W) complexes
Kayran, C; Rouzi, P (Walter de Gruyter GmbH, 2001-11-01)
The thermal catalytic hydrosilylation of 1,3-butadiene (1), trans-2-methyl-1, 3-pentadiene (2), 2,3-dimethyl-1,3-butadiene (3), and isoprene (4), with triethylsilane were studied in the presence of M(CO)(3) (o-xylene) (M = Cr, Mo, W) complexes in polar and nonpolar solvents such as tetrahydrofuran, hexane and toluene. Mo(CO)(3) (o-xylene) was found to be the only active catalyst for the hydrosilylation of 3 with triethylsilane, which gave 1-triethylsilyl-2,3-dimethyl-2-butene (3a), as hydrosilylated product...
Asymmetric benzoin reaction catalyzed by benzoylformate decarboxylase
Demir, Ayhan Sıtkı; Dunnwald, T; Iding, H; Pohl, M; Muller, M (1999-12-17)
Aromatic aldehydes are converted into benzoins by benzoylformate decarboxylase catalyzed C-C bond formation. The reaction affords (R)-benzoins with high enantiomeric excess and in good chemical yields. A broad range of aromatic aldehydes can be used as substrates in aqueous buffer or buffer/DMSO-solutions.
Citation Formats
T. Dunnwald, A. S. Demir, P. Siegert, M. Pohl, and M. Muller, “Enantioselective synthesis of (S)-2-hydroxypropanone derivatives by benzoylformate decarboxylase catalyzed C-C bond formation,” EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, pp. 2161–2170, 2000, Accessed: 00, 2020. [Online]. Available: https://hdl.handle.net/11511/53993.