Combination of stereospecific dihydroxylation and enzyme catalyzed enantioselective resolution for synthesis of enantiopure vicinal diols

Moen, Anders; Ruud, Kjersti; Anthonsen, T.

doi:10.1016/j.molcatb.2007.09.003

Cited by 10 publications

(8 citation statements)

References 23 publications

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“…CALA shows high enantioselectivity for phenyl-(2-naphthyl)-methanol (6) (one phenyl and one naphthyl group connected to the stereocenter) which is in accordance with previous reported results. [11][12][13][14][15][16] Experimental Section…”

Section: Discussionmentioning

confidence: 99%

“…[6][7][8][9][10] Lipase A from this fungus (CALA) is reported to show broad catalytic activity towards a diversity of sterically hindered alcohols, including both secondary and tertiary alcohols. [11][12][13][14][15][16] It was interesting to investigate whether this lipase could catalyze resolutions of secondary alcohols with phenyl and naphthyl groups and other bulky groups attached to the stereocenter. The 3D structure of CALA has not been published, however, the structure of the lipase has recently been predicted by comparative modeling and site directed mutagenesis.…”

Section: Introductionmentioning

confidence: 99%

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Biocatalytic synthesis of saphenic acid enantiomers

Tjosås¹,

Anthonsen²,

Jacobsen³

2008

Arkivoc

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Efficient methods for kinetic resolution of saphenic acid (2) and phenyl-(2-naphthyl)-methanol (6) have been developed using lipases B and A from Candida antarctica, respectively, as catalysts. Lipase B from Candida antarctica showed high enantioselectivity in esterification with vinyl butanoate of the alcohol 2. By subsequent crystallization, the enantiomeric excess, ee, of (S)-saphenic acid ((S)-2) was higher than earlier reported. The butanoate (R)-4 was obtained in high enantiopurity by esterification of the alcohol 2. The enantiopure alcohol (R)-2 and the butanoate (S)-4 were synthesized by CALB catalyzed hydrolysis of 4 (the butanoate of 2).Lipase A from Candida antarctica showed high enantioselectivity in esterification of the alcohol 6 with vinyl acetate, and both (S)-phenyl-(2-naphthyl)-methanol ((S)-6) and the (R)-acetate of phenyl-(2-naphthyl)-methanol ((R)-7) were obtained in high enantiomeric excess. The corresponding (R)-phenyl-(2-naphthyl)-methanol ((R)-6) and the (S)-acetate of phenyl-(2-naphthyl)-methanol ((S)-7) were obtained by CALA-catalyzed hydrolysis of the acetate of phenyl-(2-naphthyl)-methanol (7).

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Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Biocatalytic synthesis of saphenic acid enantiomers

Tjosås¹,

Anthonsen²,

Jacobsen³

2008

Arkivoc

Self Cite

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“…In literature,t here is ar eport on Os-catalyzed AD of amethyl cinnamate a26 to give d26 in 85 % ee, [17] together with two reports involving the AD reactions of the ethyl [33] and naphthyl [33a] counterparts of a26 catalyzed by AD-mix, [33] but examples of metal-catalyzed AD of b-methyl cinnamates,t o our best knowledge,have not been reported, despite areport involving non-enantioselective cis-dihydroxylation of a20 with H 2 O 2 catalyzed by [Fe II ( 5-tips3 tpa)(OTf) 2 ]( 5-tips3 tpa = a triply iPr 3 Si-substituted tris(2-pyridylmethyl)amine ligand) [5i] and afew reports on non-enantioselective cis-dihydroxylation of b-methyl cinnamates with N-methylmorpholine N-oxide (NMO) catalyzed by Os compounds. [34] TheA Dr eactions of Z-trisubstituted alkenes a28, a29, and a31 by H2 1/H 2 O 2 afforded the cis-diols with good-toexcellent enantioselectivity (81-97 % ee)and 83-90 % cis-diol selectivities (Table 4). An excellent enantioselectivity of 97 % ee was achieved for the phenyl angelate a28 (87 % cis-diol selectivity;entry 1inT able 4);this stereoselectivity is higher than that reported for the analogues of a28 using AD-mix-b or AD-mix-a catalyst (90:10 dr for (À)-menthyl angelate, [10] 60-90 % ee for methyl, i-butyl, and p-methoxybenzyl angelates [28e] ).…”

Section: Angewandte Chemiementioning

confidence: 99%

Iron‐Catalyzed Highly Enantioselective cis‐Dihydroxylation of Trisubstituted Alkenes with Aqueous H₂O₂

Wei

Wang

et al. 2020

Angewandte Chemie

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Reliable methods for enantioselective cis‐dihydroxylation of trisubstituted alkenes are scarce. The iron(II) complex cis‐α‐[FeII(2‐Me2‐BQPN)(OTf)2], which bears a tetradentate N4 ligand (Me2‐BQPN=(R,R)‐N,N′‐dimethyl‐N,N′‐bis(2‐methylquinolin‐8‐yl)‐1,2‐diphenylethane‐1,2‐diamine), was prepared and characterized. With this complex as the catalyst, a broad range of trisubstituted electron‐deficient alkenes were efficiently oxidized to chiral cis‐diols in yields of up to 98 % and up to 99.9 % ee when using hydrogen peroxide (H2O2) as oxidant under mild conditions. Experimental studies (including 18O‐labeling, ESI‐MS, NMR, EPR, and UV/Vis analyses) and DFT calculations were performed to gain mechanistic insight, which suggested possible involvement of a chiral cis‐FeV(O)2 reaction intermediate as an active oxidant. This cis‐[FeII(chiral N4 ligand)]2+/H2O2 method could be a viable green alternative/complement to the existing OsO4‐based methods for asymmetric alkene dihydroxylation reactions.

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“…To improve the interpretation of the kinetic resolution of tertiary alcohols, the thermodynamic analysis can be applied as efficient tools. However, a few papers dealing with the enzymatic resolution of tertiary alcohol have been published [7][8][9].…”

Section: Introductionmentioning

confidence: 99%

Lipase-catalyzed remote kinetic resolution of citalopram intermediate by asymmetric alcoholysis and thermodynamic analysis

Wang

et al. 2012

Bioprocess Biosyst Eng

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Lipase-catalyzed remote resolution of the tertiary alcohol, citalopram intermediate (diol acetate), has been achieved. The chiral discrimination was obtained by the Novozym435-catalyzed alcoholysis of the primary hydroxyl ester which was four bonds away from the center. The influence of acyl acceptor structure and the organic solvents on the reaction rate and enantioselectivity were investigated. Based on the thermodynamic analysis, the difference of activation free energy between the two enantiomers which dominated the enantioselectivity was significantly affected by the organic solvents, while the acyl acceptor showed less effect. In addition, the enantiomer discrimination was driven by both the difference of activation enthalpy and activation entropy. The thermodynamic analysis provides further insights into the prediction and optimization of enantioselectivity and reaction rate in remote resolution.

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Combination of stereospecific dihydroxylation and enzyme catalyzed enantioselective resolution for synthesis of enantiopure vicinal diols

Cited by 10 publications

References 23 publications

Biocatalytic synthesis of saphenic acid enantiomers

Biocatalytic synthesis of saphenic acid enantiomers

Iron‐Catalyzed Highly Enantioselective cis‐Dihydroxylation of Trisubstituted Alkenes with Aqueous H₂O₂

Lipase-catalyzed remote kinetic resolution of citalopram intermediate by asymmetric alcoholysis and thermodynamic analysis

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Combination of stereospecific dihydroxylation and enzyme catalyzed enantioselective resolution for synthesis of enantiopure vicinal diols

Cited by 10 publications

References 23 publications

Biocatalytic synthesis of saphenic acid enantiomers

Biocatalytic synthesis of saphenic acid enantiomers

Iron‐Catalyzed Highly Enantioselective cis‐Dihydroxylation of Trisubstituted Alkenes with Aqueous H2O2

Lipase-catalyzed remote kinetic resolution of citalopram intermediate by asymmetric alcoholysis and thermodynamic analysis

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Iron‐Catalyzed Highly Enantioselective cis‐Dihydroxylation of Trisubstituted Alkenes with Aqueous H₂O₂