Show/Hide Menu
Hide/Show Apps
Logout
Türkçe
Türkçe
Search
Search
Login
Login
OpenMETU
OpenMETU
About
About
Open Science Policy
Open Science Policy
Communities & Collections
Communities & Collections
Help
Help
Frequently Asked Questions
Frequently Asked Questions
Guides
Guides
Thesis submission
Thesis submission
MS without thesis term project submission
MS without thesis term project submission
Publication submission with DOI
Publication submission with DOI
Publication submission
Publication submission
Supporting Information
Supporting Information
General Information
General Information
Copyright, Embargo and License
Copyright, Embargo and License
Contact us
Contact us
Enantioselective synthesis of (S)-2-hydroxypropanone derivatives by benzoylformate decarboxylase catalyzed C-C bond formation
Date
2000-06-01
Author
Dunnwald, T
Demir, Ayhan Sıtkı
Siegert, P
Pohl, M
Muller, M
Metadata
Show full item record
This work is licensed under a
Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License
.
Item Usage Stats
30
views
0
downloads
Cite This
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.
Subject Keywords
Enzymes
,
Asymmetric synthesis
,
C-C coupling
,
Cyclodextrins
,
Carboligation
URI
https://hdl.handle.net/11511/53993
Journal
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
Collections
Department of Chemistry, Article
Suggestions
OpenMETU
Core
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
IEEE
ACM
APA
CHICAGO
MLA
BibTeX
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.