Abstract
For the first time, dehydroabietane-derived alcohols containing an OH group at the C-7 position were used to produce thioacetates by direct ZnCl2-catalyzed substitution of the hydroxyl group. Thioacetates obtained were found to give the corresponding disulfides when treated with MeONa in the presence of atmospheric oxygen with no observation of any thiol formation. In addition, the ability of diol with two hydroxyl groups at C-7 and C-18 to be converted to a cyclic dimer was detected. Dehydroabietane derivatives with a sulfur atom at the C-7 position (thiol, disulfides), which are promising for the production of biologically active substances, were first obtained.
Graphical abstract
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Ito Y, Shibata K, Hongo A, Kinoshita M (1998) Ecabet sodium, a locally acting antiulcer drug, inhibits urease activity of Helicobacter pylori. Eur J Pharmacol 345:193–198. https://doi.org/10.1016/s0014-2999(97)01622-1
Iwamoto M, Minami T, Tokuda H, Ohtsu H, Tanaka R (2003) Potential antitumor promoting diterpenoids from the stem bark of Thuja standishii. Planta Med 69:69–72. https://doi.org/10.1055/s-2003-37037
Izmest'ev YeS, Pestova SV, Lezina OM, Rubtsova SA, Kutchin AV (2019) Synthesis of novel chiral 18-sulfanyl and sulfonyl dehydroabietane derivatives. ChemistrySelect 4:11034–11037. https://doi.org/10.1002/slct.201902600
Krohn K, Budianto E, Flörke U, Hausen BM (1992) Untersuchung der allergenen Prinzipien aus Kolophonium: Autoxidation, Synthese und Sensibilisierung. Liebigs Ann Chem 1992:911–919. https://doi.org/10.1002/jlac.1992199201151
Macias FA, Velasco RF, Alvarez JA, Castellano D, Galindo JCG (2004) Synthesis of melampolides and cis, cis-germacranolides as natural herbicide models. Tetrahedron 60:8477–8488. https://doi.org/10.1016/j.tet.2004.06.128
Młochowski J, Wójtowicz-Młochowska H (2015) Developments in synthetic application of selenium(IV) oxide and organoselenium compounds as oxygen donors and oxygen-transfer agents. Molecules 20:10205–10243. https://doi.org/10.3390/molecules200610205
Ohmoto T, Saito M, Yamaguchi K (1987) Constituents of Pollen. XIV. Constituents of Cedrus deodara LOUD. (3). Chem Pharm Bull 35:2443–2447. https://doi.org/10.1248/cpb.35.2443
Politi M, Braca A, Tommasi ND, Morelli I, Manunta A, Battinelli L, Mazzanti G (2003) Antimicrobial diterpenes from the seeds of Cephalotaxus harringtonia var. drupacea. Planta Med 69:468–470. https://doi.org/10.1055/s-2003-39713
Prinz S, Müllner U, Heilmann J, Winkelmann K, Sticher O, Haslinger E, Hüfner A (2002) Oxidation products of abietic acid and its methyl ester. J Nat Prod 65:1530–1534. https://doi.org/10.1021/np010656l
Rafferty RJ, Hicklin RW, Maloof KA, Hergenrother PJ (2013) Synthesis of complex and diverse compounds through ring distortion of abietic acid. Angew Chem Int Ed 53:220–224. https://doi.org/10.1002/anie.201308743
Song K-H, Oh H-M, Choi S-K, Han D-C, Kwon B-M (2005) Anti-tumor abietane diterpenes from the cones of Sequoia sempervirens. Bioorg Med Chem Lett 15:2019–2021. https://doi.org/10.1016/j.bmcl.2005.02.057
Suryawanshi SN, Rani A, Dhami TS, Bhakuni DS (1989) Studies on allylic oxidation reactions of methyl abietate. Synth Commun 19:2927–2937. https://doi.org/10.1080/00397918908052686
Ulubelen A, Topcu G, Johansson CB (1997) Norditerpenoids and diterpenoids from Salvia multicaulis with antituberculous activity. J Nat Prod 60:1275–1280. https://doi.org/10.1021/np9700681
Zhang C-L, Bie P-Y, Peng X-J, Pan X-F (2003) Total synthesis of (±)-abieta-8,11,13-trien-7β-ol. J Chin Chem Soc 50:429–432. https://doi.org/10.1002/jccs.200300066
Acknowledgements
We are grateful to the Shared-Use Equipment Center “Khimia” (Institute of Chemistry, Komi Science Center, Ural Branch, Russian Academy of Sciences) for affording the laboratory equipment. The work was carried out as a part of the Research No. FUUU-2022-0049 (Registration No. 1021062211116-4-1.4.1) and with the support of the World-class Scientific and Educational Center “Russian Arctic: New Materials, Technologies and research Methods.”
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interest
The authors declare no conflict of interest.
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
About this article
Cite this article
Izmest’ev, E.S., Pestova, S.V., Petukhov, D.V. et al. Benzylic functionalization of dehydroabietane derivatives as a convenient way to sulfur compounds. Chem. Pap. 76, 5033–5042 (2022). https://doi.org/10.1007/s11696-022-02234-9
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11696-022-02234-9