Enantioselective synthesis through microbial oxidation of arenes.  1.  Efficient preparation of terpene and prostanoid synthons

Hudlický, Tomáš; Luna, Héctor; Barbieri, G.; Kwart, L. D.

doi:10.1021/ja00222a035

Cited by 164 publications

(49 citation statements)

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“…cis-Cyclohexa-3,s-diene- 1,2-diol (1) and many of its derivatives add to ethylenic dienophiles U O H 1 mainly syn to the oxygens (8). 3 On the other hand, anti addition is predominant with a 1,2,4-triazoline-3,s-dione dienophile (lo), and singlet oxygen also adds mainly anti to the oxygen of 1 (11). The stereochemistry of the products of each of these processes has been determined in an unequivocal manner.…”

Section: Introductionmentioning

confidence: 99%

π-Facial stereoselectivity in the Diels–Alder reactions of benzene oxides

Gillard¹,

Newlands²,

Bridson³

et al. 1991

Can. J. Chem.

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. Can. J. Chem. 69, 1337 (1991). The Diels-Alder reactions of N-phenylmaleimide and dimethyl acetylenedicarboxylate with benzene oxide (1,3,5-cyclohexatriene 1,2-oxide, 3) and its more substituted derivatives 1,2-dimethyl-1,3,5-cyclohexatriene 1,2-oxide (7) and 10-oxatricyclo[4.3.1 .O]deca-2,4-diene (11) in a kinetic manner gave exclusively products of addition anti to the plane-nonsymmekical oxygen. The structures of the adducts were determined unequivocally by nuclear Overhauser enhancements in their 'H nuclear magnetic resonance spectra and by X-ray crystallographic methods. The n-facial stereoselectivity was rationalized in terms of unfavorable orbital interactions, steric hindrance between the dienophile and the syn face of benzene oxide, and a-donation by the oxygen.

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Section: Introductionmentioning

confidence: 99%

π-Facial stereoselectivity in the Diels–Alder reactions of benzene oxides

Gillard¹,

Newlands²,

Bridson³

et al. 1991

Can. J. Chem.

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“…[6,7] Furthermore, ROs were shown to be suitable for bioremediation applications and to have the ability to process xenobiotics. [8,9] In industry, ROs are utilized to manufacture the blue dye indigo, which is crucial for the production of denim cloth.[10]Oxygen-dependent ROsn ot only convert ah uge variety of compounds, but these catalysts also displayabroad reaction scope. With these enzymes ystems it is possible to address monohydroxylations( Scheme 1, path I), dihydroxylations (Scheme 1, path II), and O-dealkylations (Scheme 1, path III) with high regio-a nd stereoselectivities.…”

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confidence: 99%

Semirational Engineering of the Naphthalene Dioxygenase from Pseudomonas sp. NCIB 9816‐4 towards Selective Asymmetric Dihydroxylation

2017

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Enzyme-catalyzed asymmetric dihydroxylation is ap owerful tool fort he selective oxyfunctionalization of various organic compounds. By applying Rieske non-heme dioxygenases (ROs), molecular oxygen and ar eduction equivalent are needed for the generation of vicinal cis-diols. We report ac omprehensive mutagenesis study of the active site of the naphthalene dioxygenasef rom Pseudomonas sp. NCIB 9816-4 comprising 62 variants. We aimed to understand the important structure-function relationships by investigating different substituted arene substrates and the geometry of the active site. Introducing single-point mutations at positions F202, A206, V260, H295, F352, and L307 resulted in drastic shifts in the reactions pecificity,r egioselectivity,a nd stereoselectivity (! 90 %) while maintaining the residual activity towards the natural substrate naphthalene.One of the key reactions in chemistryi st he selective oxyfunctionalization of organic compounds. In this context, chiralv icinal 1,2-diols are of particular interest and are often applied as chiral ligands, auxiliaries, and chiral synthons for pharmaceuticals and agrochemicals.[1] These functionalized compounds are generated by multicomponent Rieske non-heme dioxygenases (ROs), which, analogously to some P450sm onooxygenases, consist of ar eductase, af erredoxin, andahexameric oxygenase.[2] In ROs, categorized as types III and IV,t he reductase obtains electrons from the naturalc osubstrate NAD(P)H,a nd a ferredoxin component shuttles electrons from the reductase to the oxygenase active site, at which actual oxygen activation and substrate hydroxylation occur. [3,4] Representing ab iocatalytic alternative to asymmetricd ihydroxylation with toxic transition-metal catalysts, ROs also exhibit ab road substrate scope.[5] Over 300 diverse substrates ranging from polyaromatic hydrocarbons such as phenanthracene to halogenated ethylenes and flavonoid structures were reportedt ob eh ydroxylated with these enzymes. [6,7] Furthermore, ROs were shown to be suitable for bioremediation applications and to have the ability to process xenobiotics. [8,9] In industry, ROs are utilized to manufacture the blue dye indigo, which is crucial for the production of denim cloth.[10]Oxygen-dependent ROsn ot only convert ah uge variety of compounds, but these catalysts also displayabroad reaction scope. With these enzymes ystems it is possible to address monohydroxylations( Scheme 1, path I), dihydroxylations (Scheme 1, path II), and O-dealkylations (Scheme 1, path III) with high regio-a nd stereoselectivities. [11,12] Recently,s emirational engineering of the cumene dioxygenase (CDO) from Pseudomonas fluorescens IP01 expanded the substrate scope of these versatile catalysts to ar ange of sterically demanding cyclic and linear alkenesa nd monoterpenes. The CDOs ingle variant M232Aw as able to convert different terpeneg eometries such as myrcene and (À)-a-pinene with high specificity and selectivity. [13] This work motivated us to gain furtheri nsighti nto crucial structure-function relation...

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“…It is noteworthy that both the mono-and dihydroxylation products 11 and 10, obtained using TDO, had identical absolute configurations to those obtained earlier (8a -c and 7a -c) using the same biocatalyst and the corresponding unsubstituted benzocycloalkenes 6a -c (Scheme 2). [10,12,13,18,19] FULL PAPERS Derek R. Boyd et al When the biotransformation of 2-methylindene 9 was repeated using P putida NCIMB 8859 (NDO) , benzylic hydroxylation was found to be dominant and (1S)-2-methylinden-1-ol 11 was isolated in good yield (67%, > 98% ee) without isomerisation to ketone 12. Isomerisation of the enantiopure compound, under mild basic conditions, yielded ketone 12 which was again found to have racemised spontaneously.…”

Section: Alkenementioning

confidence: 99%

Biocatalytic Asymmetric Dihydroxylation of Conjugated Mono‐ and Poly‐alkenes to Yield Enantiopure Cyclic cis‐Diols

et al. 2005

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Dioxygenase-catalysed asymmetric dihydroxylation, of a series of conjugated monoalkenes and polyenes, was found to yield the corresponding monols and 1,2-dihydrodiols. The diol metabolites were obtained from monosubstituted, gem-disubstituted, cis-disubstituted, and trisubstituted alkene substrates, using whole cells of Pseudomonas putida strains containing toluene and naphthalene dioxygenases. Dioxygenase selection and alkene type were established as important factors, in the preference for dioxygenase-catalysed 1,2-dihydroxylation of conjugated alkene or arene groups, and monohydroxylation at benzylic or allylic centres. Competition from allylic hydroxylation of methyl groups was observed only when naphthalene dioxygenase was used as biocatalyst. The structures, enantiomeric excess values and absolute configurations of the bioproducts, were determined by a combination of stereochemical correlation, spectroscopy (NMR and CD) and X-ray diffraction methods. cis-1,2-Diol metabolites from arenes, cyclic alkenes and dienes were generally observed to be enantiopure ( > 98% ee), while 1,2-diols from acyclic alkenes had lower enantiomeric excess values ( < 88% ee). The enantiopure cis-diol metabolite of a gem-disubstituted fulvene was used as precursor in a new chemoenzymatic route to a novel C 2 -symmetrical ketone.

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Enantioselective synthesis through microbial oxidation of arenes. 1. Efficient preparation of terpene and prostanoid synthons

Cited by 164 publications

References 0 publications

π-Facial stereoselectivity in the Diels–Alder reactions of benzene oxides

π-Facial stereoselectivity in the Diels–Alder reactions of benzene oxides

Semirational Engineering of the Naphthalene Dioxygenase from Pseudomonas sp. NCIB 9816‐4 towards Selective Asymmetric Dihydroxylation

Biocatalytic Asymmetric Dihydroxylation of Conjugated Mono‐ and Poly‐alkenes to Yield Enantiopure Cyclic cis‐Diols

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