174817-06-2Relevant academic research and scientific papers
Chemoenzymatic synthesis of trans -tetrahydrofuran cores of annonaceous acetogenins from bromobenzene
Ramos, Juan Carlos,Brovetto, Margarita,Seoane, Gustavo A.
supporting information, p. 1982 - 1985 (2013/06/05)
Two types of trans-THF cores, present in acetogenins, have been synthesized by an intramolecular iodoetherification reaction. The starting alkenol was obtained in a few steps from a chiral cis-diol resulting from microbial oxidation of bromobenzene. The cyclization gave complete stereoselectivity for trans-THF cores with either (S,S) or (R,R) configurations at the THF chiral carbons.
Total synthesis of dihydrocodeine and hydrocodone via a double claisen rearrangement and C-10/C-11 closure strategy
Varghese, Vimal,Hudlicky, Tomas
, p. 369 - 374 (2013/04/23)
Dihydrocodeine and hydrocodone were synthesized from bromobenzene in 16 and 17 transformations, respectively. The key steps involved the toluene dioxygenase-mediated dihydroxylation of bromobenzene by whole-cell fermentation with E. coli JM109(pDTG601A), Kazmaier-Claisen rearrangement of glycinate ester, Claisen rearrangement to set the C-13 quaternary center, and C-10-C-11 closure. Experimental procedures are provided for the key steps. Georg Thieme Verlag Stuttgart . New York.
Chemoenzymatic synthesis of monocyclic arene oxides and arene hydrates from substituted benzene substrates
Boyd, Derek R.,Sharma, Narain D.,Ljubez, Vera,McGeehin, Peter K. M.,Stevenson, Paul J.,Blain, Marine,Allen, Christopher C. R.
, p. 3020 - 3029 (2013/07/26)
Enantiopure cis-dihydrodiol bacterial metabolites of substituted benzene substrates were used as precursors, in a chemoenzymatic synthesis of the corresponding benzene oxides and of a substituted oxepine, via dihydrobenzene oxide intermediates. A rapid total racemization of the substituted benzene 2,3-oxides was found to have occurred, via their oxepine valence tautomers, in accord with predictions and theoretical calculations. Reduction of a substituted arene oxide to yield a racemic arene hydrate was observed. Arene hydrates have also been synthesised, in enantiopure form, from the corresponding dihydroarene oxide or trans-bromoacetate precursors. Biotransformation of one arene hydrate enantiomer resulted in a toluene-dioxygenase catalysed cis-dihydroxylation to yield a benzene cis-triol metabolite. The Royal Society of Chemistry 2013.
Chemoenzymatic synthesis of a mixed phosphine-phosphine oxide catalyst and its application to asymmetric allylation of aldehydes and hydrogenation of alkenes
Boyd, Derek R.,Bell, Mark,Dunne, Katherine S.,Kelly, Brian,Stevenson, Paul J.,Malone, John F.,Allen, Christopher C. R.
scheme or table, p. 1388 - 1395 (2012/03/27)
The chemoenzymatic synthesis of a Lewis basic phosphine-phosphine oxide organocatalyst from a cis-dihydrodiol metabolite of bromobenzene proceeds via a palladium-catalysed carbon-phosphorus bond coupling and a novel room temperature Arbuzov [2,3]-sigmatropic rearrangement of an allylic diphenylphosphinite. Allylation of aromatic aldehydes were catalysed by the Lewis basic organocatalyst giving homoallylic alcohols in up to 57% ee. This compound also functioned as a ligand for rhodium-catalysed asymmetric hydrogenation of acetamidoacrylate giving reduction products with ee values of up to 84%.
Chemoenzymatic formal synthesis of (-)- and (+)-epibatidine
Boyd, Derek R.,Sharma, Narain D.,Kaik, Magdalena,McIntyre, Peter B. A.,Stevenson, Paul J.,Allen, Christopher C. R.
, p. 2774 - 2779,6 (2020/08/31)
The cis-dihydrocatechol, derived from enzymatic cis-dihydroxylation of bromobenzene using the microorganism Pseudomonas putida UV4, was converted into (-)-epibatidine in eleven steps with complete stereocontrol. In addition, an unprecedented palladium-catalysed disproportionation reaction gave the (+)-enantiomer of an advanced key intermediate employed in a previous synthesis of epibatidine.
Structure, stereochemistry and synthesis of enantiopure cyclohexenone cis-diol bacterial metabolites derived from phenols
Boyd, Derek R.,Sharma, Narain D.,Malone, John F.,McIntyre, Peter B. A.,Stevenson, Paul J.,Allen, Christopher C. R.,Kwit, Marcin,Gawronski, Jacek
scheme or table, p. 6217 - 6229 (2012/09/05)
Biotransformation of 3-substituted and 2,5-disubstituted phenols, using whole cells of P. putida UV4, yielded cyclohexenone cis-diols as single enantiomers; their structures and absolute configurations have been determined by NMR and ECD spectroscopy, X-ray crystallography, and stereochemical correlation involving a four step chemoenzymatic synthesis from the corresponding cis-dihydrodiol metabolites. An active site model has been proposed, to account for the formation of enantiopure cyclohexenone cis-diols with opposite absolute configurations.
Cycloalkenyl halide substitution reactions of enantiopure arene cis-tetrahydrodiols with boron, nitrogen and phosphorus nucleophiles
Boyd,Sharma,Kaik,Bell,Berberian,McIntyre,Kelly,Hardacre,Stevenson,Allen
experimental part, p. 2455 - 2465 (2011/11/04)
Enantiopure arene cis-tetrahydrodiols of bromobenzene and iodobenzene have been obtained in good yields, from chemoselective hydrogenation (rhodium-graphite) of the corresponding cis-dihydrodiol metabolites. Palladium-catalysed substitution of the halogen, by hydrogen, boron, nitrogen and phosphorus nucleophiles, in the acetonide derivatives, has yielded highly functionalised products for application in synthesis with potential as scaffolds for chiral ligands. Copyright
Investigation of steric and functionality limits in the enzymatic dihydroxylation of benzoate esters. Versatile intermediates for the synthesis of pseudo-sugars, amino cyclitols, and bicyclic ring systems
Fabris, Fabrizio,Collins, Jonathan,Sullivan, Bradford,Leisch, Hannes,Hudlicky, Tomas
experimental part, p. 2619 - 2627 (2009/10/30)
A series of benzoate esters (methyl, ethyl, n-Pr, i-Pr, n-Bu, t-Bu, allyl, and propargyl) were subjected to enzymatic dihydroxylation by E. coli JM 109(pDTG 601) strain in a whole-cell fermentation. The cis-cyclohexadienediols were obtained in yields of ～1g/L except for n-propyl- and i-propyl benzoate which were found to be poor substrates. n-Butyl and t-butyl benzoates were not oxidized at all. The absolute stereochemistry for all metabolites was determined by comparison with a standard prepared from (1S-cis)-3-bromo-3,5- cyclohexadiene-1,2-diol, whose absolute configuration is well established. The free diols were found to be quite stable compared to other cis-dihydrodiols of this type, however, their acetonides underwent a dimerization via a regio- and stereoselective Diels-Alder cycloaddition. The diol derived from ethyl benzoate was subjected to a stereo- and regioselective inverse electron demand Diels-Alder cycloadditions with several dienophiles. The new adducts were completely characterized. The hetero-Diels-Alder reaction of this diol with an acyl nitroso dienophile yielded regio- and stereoselectively a bicyclic oxazine, which upon reduction provided a useful derivative of amino shikimate that can be exploited in an approach to oseltamivir (Tamiflu) and other amino cyclitols. The diol was also converted to carba-α-L-galactopyranose to demonstrate its potential utility as a source of pseudo sugars. Experimental and spectral data are provided for all new compounds. The Royal Society of Chemistry 2009.
Chemoenzymatic synthesis of trans-dihydrodiol derivatives of monosubstituted benzenes from the corresponding cis-dihydrodiol isomers
Boyd, Derek R.,Sharma, Narain D.,Llamas, Nuria M.,Coen, Gerard P.,McGeehin, Peter K. M.,Allen, Christopher C. R.
, p. 514 - 522 (2008/03/14)
Enantiopure trans-dihydrodiols have been obtained by a chemoenzymatic synthesis from the corresponding cis-dihydrodiol metabolites, obtained by dioxygenase-catalysed arene cis-dihydroxylation at the 2,3-bond of monosubstituted benzene substrates. This gen
Enzymatic oxidation of thioanisoles: Isolation and absolute configuration of metabolites
Finn, Kevin J.,Cankar, Petr,Jones, Timothy R.B.,Hudlicky, Tomas
, p. 2833 - 2836 (2007/10/03)
Oxidation of p-bromothioanisole with toluene dioxygenase provides the corresponding diene diol 2 in good yield. Electrochemical reduction of 2 gives access to diene diol 3, which is not accessible by direct bio-oxidation of thioanisole. Absolute configura
