Biohydroxylations of Cbz-protected alkyl substituted piperidines by Beauveria bassiana ATCC 7159

Aitken, Suzanne J.; Grogan, Gideon; Chow, C.; Turner, Nicholas J.; Flitsch, Sabine L.

doi:10.1039/a805800h

Cited by 22 publications

(11 citation statements)

References 19 publications

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“…We initially examined the regioselectivity of the biohydroxylation of tetrahydropyran (THP) derivative 3a and found that an inseparable mixture of hydroxylated products was obtained. Studies have shown that minor alterations in substrate structure can strongly affect the selectivity of Beauveria bassiana ATCC 7159 [ 16 – 17 ]. Interestingly, the introduction of substituents on the aryl ring of some substrates can assist in directing hydroxylation away from the substituted position and can improve regioselectivity.…”

Section: Resultsmentioning

confidence: 99%

“…As reported previously with other hydroxylating systems, it is often possible to modify the selectivity of microbial hydroxylation by minor alterations of the substrate structure [ 16 – 17 ]. Although exposure of 3a to the resting cell suspension resulted in a complex mixture of hydroxylation products, compound 6 demonstrates that insertion of one methylene unit was sufficient to improve the regioselectivity dramatically.…”

Section: Resultsmentioning

confidence: 99%

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Regio- and stereoselective oxidation of unactivated C–H bonds with Rhodococcus rhodochrous

O’Reilly

Aitken²,

Grogan³

et al. 2012

Beilstein J. Org. Chem.

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SummaryThe ability of Rhodococcus rhodochrous (NCIMB 9703) to catalyse the regio- and stereoselective hydroxylation of a range of benzyloxy-substituted heterocycles has been investigated. Incubation of 2-benzyloxytetrahydropyrans with resting cell suspensions of the organism yielded predominantly a mixture of 5-hydroxylated isomers in combined yields of up to 40%. Exposure of the corresponding 2-benzyloxytetrahydrofuran derivatives to the cell suspensions gave predominantly the 4-hydroxylated isomers in yields of up to 26%. Most interestingly, 2-(4-nitrobenzyloxy)tetrahydrofuran and 2-(4-nitrobenzyloxy)tetrahydropyran were transformed in high yields to the 4-hydroxylated and 5-hydroxylated products, respectively.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Regio- and stereoselective oxidation of unactivated C–H bonds with Rhodococcus rhodochrous

O’Reilly

Aitken²,

Grogan³

et al. 2012

Beilstein J. Org. Chem.

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“…(trans-1,4-Cyclohexanol methanesulfonyl)phosphoramidic Acid Diethyl Ester (10). Elution with 95:5 methylene chloride-methanol afforded 10 as white, needlelike crystals: yield 2.47 g (62%); R f 0.42 (9:1 chloroform-methanol); mp 70-71°C; 1 ,40.12;H,7.34;N,4.25.…”

Section: Methodsmentioning

confidence: 99%

Syntheses of New Phosphorus-Containing Azabicycloalkanes and Their Microbial Hydroxylation Using Beauveria bassiana

Hemenway

Olivo

1999

J. Org. Chem.

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Representative novel phosphorus-containing azabicyclic substrates have been synthesized and subsequently microbially hydroxylated in fair to good yields using the microorganism Beauveria bassiana. (7-Azabicyclo[2.2.1]hept-7-yl)phosphonic acid diethyl ester was hydroxylated at the unactivated methylene carbon to give (2-endo-hydroxy-7-azabicyclo[2.2.1]hept-7-yl)phosphonic acid diethyl ester in 43% yield and 64% ee, while N-(diphenylphosphinoyl)-7-azabicyclo[2.2.1]heptane was similarly hydroxylated to give 2-endo-hydroxy-7-(diphenylphosphinoyl)-7-azabicyclo[2.2.1]-heptane in 35% yield and 20% ee. (7-Azabicyclo[2.2.1]hept-7-yl)phosphonic acid diphenyl ester yielded two distinct hydroxylated products: monohydroxylated (2-endo-hydroxy-7-azabicyclo[2.2.1]-hept-7-yl)phosphonic acid diphenyl ester in 7% yield and 7% ee and dihydroxylated (2-endo-hydroxy-7-azabicyclo[2.2.1]hept-7-yl)phosphonic acid phenyl, p-hydroxyphenyl ester in 37% yield and 77% ee. HPLC studies indicated that the monohydroxylated metabolite is formed first during fermentation, and becomes a substrate for a second enzymatic hydroxylation at one of the aromatic rings with induced enantioselection, to give the dihydroxylated metabolite. All microbially hydroxylated metabolites were easily N-deprotected using TFA-CH 2 Cl 2 (1:1). Thus, N-phosphinyl groups are good facilitators of hydroxylation reactions with B. bassiana and offer a new choice for an N-substituent when substrates are hydroxylated with this microorganism. By offering a new N-substituent, this work extends the general utility of B. bassiana as a preparatively useful unactivated methylene hydroxylator.

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“…A comparison of the hydroxylated products from both series of substrates (Cbz and benzoyl protected) is shown in Table 2 (17). The protected parent piperidine derivatives 7 and 11 gave both 4-hydroxylated products, but with several of the alkyl substituted piperidines a significant change in the regioselectivity of hydroxylation was observed.…”

Section: Biohydroxylations Using B Bassianamentioning

confidence: 97%

Biohydroxylation Reactions Catalyzed by Enzymes and Whole-Cell Systems

Flitsch

Aitken

Chow

et al. 1999

Bioorganic Chemistry

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Biohydroxylations of Cbz-protected alkyl substituted piperidines by Beauveria bassiana ATCC 7159

Cited by 22 publications

References 19 publications

Regio- and stereoselective oxidation of unactivated C–H bonds with Rhodococcus rhodochrous

Regio- and stereoselective oxidation of unactivated C–H bonds with Rhodococcus rhodochrous

Syntheses of New Phosphorus-Containing Azabicycloalkanes and Their Microbial Hydroxylation Using Beauveria bassiana

Biohydroxylation Reactions Catalyzed by Enzymes and Whole-Cell Systems

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