Subscribe to RSS
Please copy the URL and add it into your RSS Feed Reader.
https://www.thieme-connect.de/rss/thieme/en/10.1055-s-00000084.xml
Synthesis 2019; 51(09): 1995-2000
DOI: 10.1055/s-0037-1610686
DOI: 10.1055/s-0037-1610686
paper
Selectivity Control in Terpene Rearrangements: A Biomimetic Synthesis of the Halimanic Bicyclic Core
Financial support from the Supreme Council for Science and Technology Development, Academy of Sciences of Moldova (Project No. 15.817.02.14A) is gratefully acknowledged. V.K. acknowledges the Alexander von Humboldt Foundation for a postdoctoral fellowship.Further Information
Publication History
Received: 18 September 2018
Accepted after revision: 17 December 2018
Publication Date:
19 February 2019 (online)
Abstract
The bicyclic core of the halimanic framework is synthesized in optically active form by an acid-induced rearrangement of a homodrimanic epoxide. The substrate can follow two different pathways under acidic treatment. Using fluorosulfonic acid as a promoter at low temperature favors ring contraction to a perhydrindanic structure. In contrast, milder acids at higher temperatures bring about predominantly an angular methyl migration and formation of the halimanic bicyclic system. In particular, an acidic pillared clay selectively promoted this transformation.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0037-1610686.
- Supporting Information
-
References
- 1 Current address: Innotech Alberta, Hwy 16A & 75 Street, Vegreville, Alberta, T9C 1T4, Canada.
- 2 Current address: Flumed-Farm S.R.L., str. Cetatea Albă 176, Chişinău MD-2002, Republic of Moldova.
- 3 Kulcitki V, Ungur N, Gavagnin M, Carbone M, Cimino G. Tetrahedron: Asymmetry 2004; 15: 423
- 4 Kulciţki V, Sîrbu T, Ungur N. Chem. J. Mold. Gen., Ind. Ecol. Chem. 2011; 6: 110
- 5 Roncero AM, Tobal IE, Moro RF, Díez D, Marcos IS. Nat. Prod. Rep. 2018; 35: 955
- 6 Peters RJ. Nat. Prod. Rep. 2010; 27: 1521
- 7 Yong KW. L, Jankam A, Hooper JN. A, Suksamrarn A, Garson MJ. Tetrahedron 2008; 64: 6341
- 8 Hoshino T, Nakano C, Ootsuka T, Shinohara Y, Hara T. Org. Biomol. Chem. 2011; 9: 2156
- 9 Marcos I, Conde A, Moro R, Basabe P, Díez D, Mollinedo F, Urones J. Molecules 2008; 13: 1120
- 10 Favier LS, Nieto M, Giordano OS, Tonn CE. Phytochemistry 1997; 45: 1469
- 11 Ono M, Ito Y, Nohara T. Chem. Pharm. Bull. 2001; 49: 1220
- 12 Nagashima F, Suzuki M, Takaoka S, Asakawa Y. J. Nat. Prod. 2001; 64: 1309
- 13 Ono M, Yanaka T, Yamamoto M, Ito Y, Nohara T. J. Nat. Prod. 2002; 65: 537
- 14 Yoon T, Danishefsky SJ, de Gala S. Angew. Chem., Int. Ed. Engl. 1994; 33: 853
- 15 Maugel N, Mann FM, Hillwig ML, Peters RJ, Snider BB. Org. Lett. 2010; 12: 2626
- 16 Mann FM, Peters RJ. Med. Chem. Commun. 2012; 3: 899
- 17 Salmoun M, Braekman JC, Dewelle J, Darro F, Kiss R, De Voogd NJ, Van Soest RW. M. Nat. Prod. Res. 2007; 21: 149
- 18 Carr G, Raszek M, Van Soest R, Matainaho T, Shopik M, Holmes CF. B, Andersen RJ. J. Nat. Prod. 2007; 70: 1812
- 19 de Miranda DS, da Conceição GJ. A, Zukerman-Schpector J, Guerrero MC, Schuchardt U, Pinto AC, Rezende CM, Marsaioli AJ. J. Braz. Chem. Soc. 2001; 12: 391
- 20 George JH, McArdle M, Baldwin JE, Adlington RM. Tetrahedron 2010; 66: 6321
- 21 Kuan KK. W, Pepper HP, Bloch WM, George JH. Org. Lett. 2012; 14: 4710
- 22 Wang J.-L, Li H.-J, Wang M, Wang J.-H, Wu Y.-C. Tetrahedron Lett. 2018; 59: 945
- 23 Kulciţki V, Ungur N, Gavagnin M, Carbone M, Cimino G. Eur. J. Org. Chem. 2005; 1816
- 24 Kulciţki V. Acta Biochim. Pol. 2007; 54: 679
- 25 Rusu V, Maftuleac A, Petuhov O, Kulciţki V, Grinco M, Postolachi L, Rusu M. Studia Universitatis Moldaviae (Real and Nature Sciences) 2015; 178 (in Romanian)
- 26 Potter KC, Jia M, Hong YJ, Tantillo DJ, Peters RJ. Org. Lett. 2016; 18: 1060
- 27 Xu M, Jia M, Hong YJ, Yin X, Tantillo DJ, Proteau PJ, Peters RJ. Org. Lett. 2018; 20: 1200
- 28 Hadley MS, Halsall TG. J. Chem. Soc., Perkin Trans. 1 1974; 1334