Chemoenzymatic synthesis of new fragrances
- Strub, D.J.; Kula, J.; Sikora, M.; Gibka, J.; Lochynski, S., Synthesis and olfactory evaluation of homologous series of (+)- and (-)-carvone oxime ethers Flavour Frag. J. 2016, 31, 81. View at Publisher
Novel semi-synthetic fragrant compounds were prepared from both isomers of carvone.Deprotonation of (+) and (-)-carvone oximes with sodium hydride and subsequent O-Alkylation with various alkyl halides in DMSO resulted in 18 ethers. Scents of most synthesized compounds are agreeable. A shift of fragrance is observed between substrates. The scent of (-)-carvone resembles that of spearmint and (+)-carvone – caraway. The fragrance of carvone oximes is similar, vegetable-like. Significant differences were observed between homologous series of carvone oxime ethers. Their odours range from vegetable-like (pickled cucumber, leaves of horseradish and carrot, scallion and onion) and herbaceous to sulphuric, floral (lily) and fruity (blackcurrant and pear)..
- Strub, D., Balcerzak, L., Lochyński, S., (+)-3-Carene: valuable starting material for synthesis of low-molecular compounds with olfactory properties Curr. Org. Chem. 2014, 18, 446. View at Publisher
In this article we present (+)-3-carene as a valuable source for the synthesis of compounds with various odoriferous properties.
Described compounds consist of carane, bicyclo[3.1.0]hexane, and gem-dimethylcyclohexane system in their structure. Olfactory comparative analysis with regard to the structure has been discussed. Fragrance of molecules varies from different fruit notes to floral and woody. Future prospects regarding application of biocatalysts towards synthesis of compounds with olfactory properties are briefly discussed and the synthesis details are also presented to show the simplicity of the preparation of some valuable fragrant molecules. The major part of our study has been previously described only in patents that in our opinion makes this paper a valuable data source of olfactorycharacteristics of low-molecular compounds derived from (+)-3-carene..
- Strub, D., Balcerzak, L., Niewiadomska, M., Kula, J., Sikora, M., Gibka, J., Lochyński, S., Stereochemistry of terpene derivatives. Part 8: Synthesis of terpenoids from (1S,4R)- and (1R,4S)-fenchone and their comparative odour characteristics. Tetrahedron-Asymmetr. 2014, 25, 1038. View at Publisher
O-alkylation of (+) and (−)-fenchone oximes with various alkyl halides led to 20 novel ethers. Better results were obtained when mild reaction conditions were employed (i.e., aprotic, polar solvent and room temperature). The hydrolytic kinetic resolution of the O-glycidyl derivative was carried out using cobalt-salen catalysts. The best results were obtained when using (−)-(R,R)-catalyst: (−)-(R)-isomer was obtained with >90% de. The use of a (+)-(S,S)-catalyst gave the (−)-(S)-epoxide with only 67% de. However, the (S)-epoxide was obtained with >90% de when the (−)-(R)-diol was subjected to the Mitsunobu reaction. Significant fragrance diversity was observed between the homologous series of fenchone oxime ethers. More agreeable are scents of ethers derived from (−)-fenchone oxime. Their odours range from turpentine like and resinous to vegetable, floral or woody whereas the scents of (+)-ethers range from turpentine, resinous to onion like and slightly floral..
- Kuriata-Adamusiak, R., Strub, D., Lochyński, S., Application of microorganisms towards synthesis of chiral terpenoid derivatives. Appl. Microbiol. Biot. 2012, 95, 1427. View at Publisher
Biotransformations are a standard tool of green chemistry and thus are following the rules of sustainable development. In this article, we describe the most common types of reactions conducted by microorganisms applied towards synthesis of chiral terpenoid derivatives. Potential applications of obtained products in various areas of industry and agriculture are shown. We also describe biological activity of presented compounds. Stereoselective hydroxylation, epoxidation, Baeyer-Villiger oxidation, stereo- and enantioselective reduction of ketones, and various kinetic resolutions carried out by bacteria and fungi have been reviewed. Mechanistic considerations regarding chemical and enzymatic reactions are presented. We also briefly describe modern approaches towards enhancing desired enzymatic activity in order to apply modified biocatalysts as an efficient tool and green alternative to chemical catalysts used in industry..
- Kuriata-Adamusiak, R., Strub, D., Szatkowski, P., Lochyński, S., Biotransformation of bicyclic terpenoid ketones towards new compounds with olfactory properties. Flavour Fragr. J. 2011, 26, 351. View at Publisher
In the search of new chiral derivatives with olfactory properties we performed stereoselective reactions mediated by different strains of microorganisms such as Aspergillus niger, Fusarium oxysporum, Fusarium culmorum, Hansenula anomala and Streptomyces lusitanus StA. Oxidation of (+)-3-carene with O2 and CrO3 led to (+)-3-carene-5-one and (−)-3-carene-2,5-dione, which were used as substrates for biotransformation. As a result, five odoriferous derivatives were characterized by spectroscopic methods. This is the first time that their olfactory properties have been determined. 3,6,6-trimethylcyclohept-2-en-1-one is described as balsamic with a turpentine note, whereas the odour of 3,6,6-trimethyl-cyclohept-2-en-1-one is described as vegetable, celery–parsley–lovage. An uncommon and valuable application of Streptomyces has been presented..
- Kuriata, R., Gajcy, K., Turowska-Tyrk, I., Lochyński, S.;, Stereochemistry of terpene derivatives. Part 6: Chemoenzymatic synthesis of chiral bicyclo[3.1.0]hexane derivatives with olfactory properties. Tetrahedron: Asymetry 2010, 21, 805
Starting from (+)-3-carene 1 several chiral fragrant compounds with the bicyclo[3.1.0]hexane system were synthesized. These compounds were used as substrates for biotransformation with lipases as biocatalysts. Pure diastereoisomers were obtained and their absolute configuration was confirmed by X-ray crystallography. The olfactory properties of new compounds were determined..
- Frackowiak, B.; Olejniczak, T.; Latajka, R.; Bialonska, A.; Ciunik, Z.; Lochynski, S. , Stereochemistry of terpene derivatives. Part 4: Fragrant terpenoid derivatives with an unsaturated gem-dimethylbicyclo[3.1.0]hexane system. Tetrahedron: Asymmetry 2005, 16, 3352
Starting from (+)-3-carene I several chiral fragrant compounds with the bicyclo[3.1.0]hexane system 4-6 and 10-20 were synthesized. These compounds are structural analogues of naturally occurring fragrant compounds, such as ionones and damascones, and possess either an endo- or an exo-cyclic double bond in the bicyclo[3.1.0]hexane moiety. The absolute configuration of selected products was confirmed by X-ray crystallography and circular dichroism analysis..
- Lochyński, S.; Kowalska, K.; Wawrzeńczyk, C., Synthesis and odour characteristics of new derivatives from the carane system. Flavour Frag. J. 2002, 17, 181
Starting from (+)-3-carene, nine new odoriferous derivatives were obtained. In comparison with (+)-3-carene, compounds synthesized contain at C-10 substituents such as methylcarbethoxy, 2-hydroxyethyl and 2-acetoxyethyl. The (+)-3-carenyl-10-acetaldehyde (10) and its acyclic and cyclic acetals were also synthesized. The odour characteristics of compounds obtained are presented. Some of them possess interesting and valuable odours; that of (+)-2-(3-caren-10-yl)ethanol (8) is described as fruity-floral with marked grapefruit note, whereas the odour of its acetate (9) is described as smoke-woody with cured bacon note..