Biotransformation of α-bromo and α,α′-dibromo alkanone to α-hydroxyketone and α-diketone by Spirulina platensis

Utsukihara, Takamitsu; Okada, Shinnosuke; Kato, Nakahide; Horiuchi, C. Akira

doi:10.1016/j.molcatb.2006.12.001

Cited by 17 publications

(7 citation statements)

References 40 publications

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“…The effective enantioselectivity of the desired product was achieved either by using whole cells of biocatalysts [ 12 , 13 , 14 , 15 , 16 ] or with the help of isolated enzymes, such as dehydrogenases [ 1 , 17 , 18 ] and lipases [ 19 ]. Although in the majority of the reported studies, the halohydrins were obtained with high substrate conversions and high enantiomeric excesses, there is always a risk of side products due to reductive dehalogenation (leading to respective 1-phenylehtan-1,2-diols) and substitution (2-hydroxyacetophenone and 1-phenylehtan-1,2-diol) [ 20 , 21 ].…”

Section: Introductionmentioning

confidence: 99%

Highly Enantioselective Production of (R)-Halohydrins with Whole Cells of Rhodotorula rubra KCh 82 Culture

Janeczko

Dymarska

Kostrzewa-Susłow

2014

IJMS

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Biotransformation of ten α-haloacetophenones in the growing culture of the strain Rhodotorula rubra KCh 82 has been carried out. Nine of the substrates underwent an effective enantioselective reduction to the respective (R)-alcohols according to Prelog’s rule, with the exception of 2-chloro-1,2-diphenylethan-1-one that was not transformed by this strain. The expected reduction proceeded without dehalogenation, leading to the respective (R)-halohydrins in high yields. The use of this biocatalyst yielded (R)-2-bromo-1-phenyl-ethan-1-ol (enantiomeric excess (ee) = 97%) and its derivatives: 4'-Bromo- (ee = 99%); 4'-Chloro- (ee > 99%); 4'-Methoxy- (ee = 96%); 3'-Methoxy- (ee = 93%); 2'-Methoxy- (ee = 98%). There were also obtained and characterized 2,4'-dichloro-, 2,2',4'-trichloro- and 2-chloro-4'-fluoro-phenyetan-1-ol with >99% of enantiomeric excesses.

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Section: Introductionmentioning

confidence: 99%

Highly Enantioselective Production of (R)-Halohydrins with Whole Cells of Rhodotorula rubra KCh 82 Culture

Janeczko

Dymarska

Kostrzewa-Susłow

2014

IJMS

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“…In a similar manner, the cyclic D-diketones 1,2-cyclooctanedione and 1,2-cyclododecanedione were synthesized in 65-71% yield from D-bromoketones [7]. It was recently shown that biotransformation of D-bromo-and D,Dc-dibromoketones formed highly selectively D-hydroxyketones and diketones, respectively [8].The goal of the present work was to synthesize secondary D-bromoketones from isopinocamphone (1), cis-verbanone (2), and menthone (3) for possible further transformation into the corresponding D-diketones. The brominating reagents were Br 2 , CuBr 2 , Meldrum's acid dibromide, and the oxidative-brominating system Ce(III)-LiBr-H 2 O 2 .…”

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confidence: 99%

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confidence: 99%

Several Monoterpenoid Bromination Products

et al. 2014

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Keywords: terpenoids, bromination, mono-and dibromo-derivatives, Meldrum's acid dibromide, oxidative brominating system.D-Dicarbonyl compounds have recently become interesting for broader application in organic synthesis because of their high reactivity. They are used to prepare aliphatic, aromatic, and heterocyclic low-and high-molecular-weight products with an array of valuable properties. Thus, several heterocyclic compounds such as imidazoles, quinoxalines, and pyrazines, i.e., a unique class of chiral N,N-coordinated ligands that are widely used in asymmetric synthesis [1,2], in addition to quinoline derivatives that usually exhibit various biological and pharmacological activities [3,4] were synthesized from terpene D-diketones.Oxidation of the corresponding D-bromoketones is one method for synthesizing D-diketones. The oxidation of 3-endo-bromocamphors by O 2 or air in aprotic polar solvents in the presence of NaI or KI to form camphoroquinone in high yield is well known [5,6]. In a similar manner, the cyclic D-diketones 1,2-cyclooctanedione and 1,2-cyclododecanedione were synthesized in 65-71% yield from D-bromoketones [7]. It was recently shown that biotransformation of D-bromo-and D,Dc-dibromoketones formed highly selectively D-hydroxyketones and diketones, respectively [8].The goal of the present work was to synthesize secondary D-bromoketones from isopinocamphone (1), cis-verbanone (2), and menthone (3) for possible further transformation into the corresponding D-diketones. The brominating reagents were Br 2 , CuBr 2 , Meldrum's acid dibromide, and the oxidative-brominating system Ce(III)-LiBr-H 2 O 2 .Attempted monobromination of isopinocamphone by Br 2 in AcOH (ketone-Br 2 mole ratio 1:1) formed mainly dibromoderivative 4 and monobromo-derivative 5 in yields of 48 and 12%, respectively, according to GC. Furthermore, the reaction products included pinocamphone (15%) and an insignificant (~2%) amount of 6. 2D,4D-Dibromopinanone-3 (4) was isolated by column chromatography over silica gel as a crystalline product. Br O Br + Br O + O Br 4 5 6 OH O a 7 1 b c 5 + 4 1 + + O Br d 9 Br O 8 Mixture of compounds a. Br 2 ; b. CuBr 2 ; c. Meldrum's acid dibromide; d. Ce(NO 3 ) 3 -LiBr-H 2 O 2

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“…Dunaliella tertiolecta (green microalga) catalyzed the biotransformation of terpenoids [12], and several keto esters were converted to the corresponding hydroxy esters by marine microalgae such Chaetoceros and Nannochloropsis [13]. The Spirulina platensis alga catalyzed alkanone debromation with good yields [14]. There are excellent studies involving the reduction of various ketones by red algae yielding enantiomerically pure alcohols [4].…”

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confidence: 99%

Bioreduction of Acetophenone Derivatives by Red Marine Algae Bostrychia radicans and B. tenella, and Marine Bacteria Associated

Mouad

Martins

Debonsi

et al. 2011

Helvetica Chimica Acta

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The biocatalytic reduction of acetophenone derivatives was exploited by using algal biomass from Bostrychia radicans and B. tenella producing exclusively (S)-2-phenylethanols with high enantiomeric excess (> 99% ee). Bacterial populations associated with algal biomass were identified as the Bacillus genus. This report deals with the first investigations involving the use of marine bacteria associated with B. radicans and B. tenella marine algae for the biocatalytic reduction of acetophenone derivatives.

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Biotransformation of α-bromo and α,α′-dibromo alkanone to α-hydroxyketone and α-diketone by Spirulina platensis

Cited by 17 publications

References 40 publications

Highly Enantioselective Production of (R)-Halohydrins with Whole Cells of Rhodotorula rubra KCh 82 Culture

Highly Enantioselective Production of (R)-Halohydrins with Whole Cells of Rhodotorula rubra KCh 82 Culture

Several Monoterpenoid Bromination Products

Bioreduction of Acetophenone Derivatives by Red Marine Algae Bostrychia radicans and B. tenella, and Marine Bacteria Associated

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