1121-63-7Relevant academic research and scientific papers
Identification and biosynthesis of tropone derivatives and sulfur volatiles produced by bacteria of the marine Roseobacter clade
Thiel, Verena,Brinkhoff, Thorsten,Dickschat, Jeroen S.,Wickel, Susanne,Grunenberg, Joerg,Wagner-Doebler, Irene,Simon, Meinhard,Schulz, Stefan
, p. 234 - 246 (2010)
Bacteria of the Roseobacter clade are abundant marine bacteria and are important contributors to the global sulfur cycle. The volatiles produced by two of its members, Phaeobacter gallaeciensis and Oceanibulbus indolifex, were analyzed to investigate whether the released compounds are derived from sulfur metabolism, and which biosynthetic pathways are involved in their formation. Both bacteria emitted different sulfides and thioesters, including new natural compounds such as 5-methyl phenylethanethioate (16) and butyl methanesulfonate (21). The S-methyl alkanoates were identified by comparison with standards that were synthesized from the respective methyl alkanoates by a new method using an easily prepared aluminium/sulfur reagent. Phaeobacter gallaeciensis is also able to produce tropone (37) in large amounts. Its biosynthesis was investigated by various feeding experiments, showing that 37 is formed via a deviation of the phenylacetate catabolism. The unstable tropone hydrate 42 was identified as an intermediate of the tropone biosynthesis that was also released together with tropolone (38). The Royal Society of Chemistry 2010.
Products from enzyme-catalyzed oxidations of norcarenes
Newcomb, Martin,Lansakara-P, Dharmika S. P.,Kim, Hye-Yeong,Chandrasena, R. Esala P.,Lippard, Stephen J.,Beauvais, Laurance G.,Murray, Leslie J.,Izzo, Viviana,Hollenberg, Paul F.,Coon, Minor J.
, p. 1128 - 1133 (2007)
(Chemical Equation Presented) Recent studies revealed that norcarane (bicyclo[4.1.0]heptane) is oxidized to 2-norcarene (bicyclo[4.1.0]-hept-2-ene) and 3-norcarene (bicyclo[4.1.0]hept-3-ene) by iron-containing enzymes and that secondary oxidation products from the norcarenes complicate mechanistic probe studies employing norcarane as the substrate (Newcomb, M.; Chandrasena, R. E. P.; Lansakara-P., D. S. P.; Kim, H.-Y.; Lippard, S. J.; Beauvais, L. G.; Murray, L. J.; Izzo, V.; Hollenberg, P. F.; Coon, M. J. J. Org. Chem. 2007, 72, 1121-1127). In the present work, the product profiles from the oxidations of 2-norcarene and 3-norcarene by several enzymes were determined. Most of the products were identified by GC and GC-mass spectral comparison to authentic samples produced independently; in some cases, stereochemical assignments were made or confirmed by 2D NMR analysis of the products. The enzymes studied in this work were four cytochrome P450 enzymes, CYP2B1, CYPΔ2E1, CYPΔ2E1 T303A, and CYPΔ2B4, and three diiron-containing enzymes, soluble methane monooxygenase (sMMO) from Methylococcus capsulatus (Bath), toluene monooxygenase (ToMO) from Pseudomonas stutzeri OX1, and phenol hydroxylase (PH) from Pseudomonas stutzeri OX1. The oxidation products from the norcarenes identified in this work are 2-norcaranone, 3-norcaranone, syn- and anti-2-norcarene oxide, syn- and anti-3-norcarene oxide, syn-and anti-4-hydroxy-2-norcarene, syn- and anti-2-hydroxy-3-norcarene, 2-oxo-3-norcarene, 4-oxo-2-norcarene, and cyclohepta-3,5-dienol. Two additional, unidentified oxidation products were observed in low yields in the oxidations. In matched oxidations, 3-norcarene was a better substrate than 2-norcarene in terms of turnover by factors of 1.5-15 for the enzymes studied here. The oxidation products found in enzyme-catalyzed oxidations of the norcarenes are useful for understanding the complex product mixtures obtained in norcarane oxidations.
trans-6-Aminocyclohept-3-enols, a new designed polyfunctionalized chiral building block for the asymmetric synthesis of 2-substituted-4-hydroxypiperidines.
Celestini, Paolo,Danieli, Bruno,Lesma, Giordano,Sacchetti, Alessandro,Silvani, Alessandra,Passarella, Daniele,Virdis, Andrea
, p. 1367 - 1370 (2002)
trans-6-Aminocyclohept-3-enols 18 and ent-18 are new designed polyfunctionalized chiral building blocks for piperidine alkaloids synthesis and are prepared in high yields from the enzymatically derived cyclohept-3-ene-1,6-diol monoacetate (-)-8. Efficient highly enantioselective syntheses of cis-4-hydroxypipecolic acid (1) and piperidines 3 and 4, in both enantiomeric forms, are described. [reaction: see text]
Total synthesis of scopine, pseudoscopine, and nor-derivatives
Justice, David E.,Malpass, John R.
, p. 11977 - 11994 (2007/10/03)
Scopine and pseudoscopine have been synthesised from cyclohepta-3,5-dienol; the initial 1,4-functionalisation of the diene is based on a nitroso- cycloaddition. The use of the N-benzyloxycarbonyl group throughout the scheme allows ultimate reductive deprotection to yield N-methyl or novel NH (nor-) derivatives without damage to the exo-epoxide of the title compounds. Preliminary investigation of nitroso- cycloaddition to 5,6-epoxycyclohepta-1,3-diene is described.
Applications of enzymes in the synthesis of bioactive polyols
Johnson, Carl R,Adams, Joseph P,Bis, Scot J,Jong, Randall L De,Golebiowski, Adam,et al.
, p. 140 - 144 (2007/10/02)
Cyclopentadiene, benzene and cycloheptatriene have been transformed to the functionalized meso-diols.The resulting meso-diols or their corresponding meso-diacetates have been subjected to enzymatic asymmetrizations using enzymes, particularly lipases, in organic or aq. media.Examples of the use of the resulting aracemic products in the synthesis of a variety of polyols of biological interest have been reviewed.
Enzymatic asymmetrization in organic media: Synthesis of unnatural glucose from cycloheptatriene
Johnson, Carl R.,Golebiowski, Adam,Steensma, Darryl H.
, p. 9414 - 9418 (2007/10/02)
Pseudomonas cepacia lipase mediated asymmetrization of a meso-3-O-protected 6-cyclohepten-1,3,5-triol using isopropenyl acetate as solvent produced optically pure monoacetate 2. Elaboration of 2 by stereoselective oxygenation of the ring system using the Rubottom reaction, diastereoselective reduction, and osmium tetroxide catalyzed cis hydroxylation lead to cycloheptanehexaol derivative 20. This cyclic polyol was transformed into an allylic alcohol which was subjected to ozonolysis followed by NaIO4 diol cleavage to give L-glucose.
Synthesis of 3,5-Dihydroxytropone
Imming, Peter,Seitz, Gunther
, p. 2183 - 2186 (2007/10/02)
Starting from tropone, the hitherto unknown 3,5-dihydroxytropone (6) is prepared in a four-step synthesis including a cycloaddition reaction of singlet oxygen. - Key Words: Cycloaddition / 3,5-Dihydroxytropone / Singlet oxygen / Y aromaticity
